Method for dyeing keratinous material, comprising the use of an organosilicon compound, a coated effect pigment and a sealing reagent i

ABSTRACT

The subject of the present disclosure is a process for dyeing keratinous material, in particular human hair, comprising the following steps:
         applying an agent (a) to the keratinous material, wherein the agent (a) comprises:   (a1) at least one organic silicon compound selected from the group of silanes having one, two or three silicon atoms, and       

     (a2) at least one coloring compound comprising at least one effect pigment comprising α) a substrate platelet and β) a coating, wherein the coating comprises at least one layer that has been wet-chemically prepared using a metal alkoxide and an organosilicon compound having a basic group; and
         applying an agent (b) to the keratinous material, wherein the agent (b) comprises:   (b1) at least one sealing reagent.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a U.S. National-Stage entry under 35 U.S.C. § 371based on International Application No. PCT/EP2020/068978, filed Jul. 6,2020, which was published under PCT Article 21(2) and which claimspriority to German Application No. 102019214286.9, filed Sep. 19, 2019,which are all hereby incorporated in their entirety by reference.

TECHNICAL FIELD

The subject of the present application is a method for treatingkeratinous material, in particular human hair, which comprises theapplication of two agents (a) and (b). The agent (a) is exemplified byits content of at least one organic silicon compound (a1) and at leastone selected coloring compound (a2) comprising at least one selectedeffect pigment. The agent (b) comprises at least one sealing reagent.

A further subject of this application is a multi-component packagingunit (kit-of-parts) for dyeing keratinous material, in particular humanhair, which comprises separately prepared at least three agent (a′),(a″) and (b). Agents (a′) and (a″) can be used to prepare the agent (a)used in the process described above.

BACKGROUND

The change in shape and color of keratin fibers, especially hair, is akey area of modern cosmetics. To change the hair color, the expert knowsvarious coloring systems depending on coloring requirements. Oxidationdyes are usually used for permanent, intensive dyeings with goodfastness properties and good grey coverage. Such dyes usually containoxidation dye precursors, so-called developer components and couplercomponents, which form the actual dyes with one another under theinfluence of oxidizing agents, such as hydrogen peroxide. Oxidation dyesare exemplified by very long-lasting dyeing results.

When direct dyes are used, ready-made dyes diffuse from the colorantinto the hair fiber. Compared to oxidative hair dyeing, the dyeingsobtained with direct dyes have a shorter shelf life and quicker washability. Dyings with direct dyes usually remain on the hair for a periodof between 5 and 20 washes.

The use of color pigments is known for short-term color changes on thehair and/or skin. Color pigments are understood to be insoluble,coloring substances. These are present undissolved in the dyeformulation in the form of small particles and are only deposited fromthe outside on the hair fibers and/or the skin surface. Therefore, theycan usually be removed without residue by a few washes withsurfactant-comprising cleaning agents. Various products of this type areavailable on the market under the name hair mascara.

If the user wants particularly long-lasting dyeings, the use ofoxidative dyes has so far been his only option. However, despitenumerous optimization attempts, an unpleasant ammonia or amine odorcannot be completely avoided in oxidative hair dyeing. The hair damagestill associated with the use of oxidative dyes also has a negativeeffect on the user's hair.

EP 2168633 B1 deals with the task of producing long-lasting haircolorations using pigments. The paper teaches that when the combinationof a pigment, an organic silicon compound, a film-forming polymer and asolvent is used on hair, it is possible to produce colorations that areparticularly resistant to shampooing.

Metallic luster pigments or metallic effect pigments are widely used inmany fields of technology. They are used, for example, to colorcoatings, printing inks, inks, plastics, glasses, ceramic products andpreparations for decorative cosmetics such as nail polish. They areexemplified by their attractive angle-dependent color impression(goniochromism) and their metallic-looking luster.

BRIEF SUMMARY

This disclosure provides a process for dyeing keratinous materialcomprising the following steps:

applying an agent (a) to the keratinous material, wherein the agent (a)comprises:

(a1) at least one organic silicon compound chosen from silanes havingone, two or three silicon atoms, and

(a2) at least one coloring compound comprising at least one effectpigment comprising α) a substrate platelet and β) a coating, wherein thecoating comprises at least one layer wet-chemically prepared using ametal alkoxide and an organosilicon compound having a basic group, and

applying an agent (b) to the keratinous material, wherein the agent (b)comprises:

(b1) at least one sealing reagent.

This disclosure also provides a kit-of-parts for dyeing keratinousmaterial, comprising separately packaged

-   -   a first container comprising an agent (a′), wherein the agent        comprises (a′):        (a1) at least one organic silicon compound chosen from silanes        having one, two or three silicon atoms, and    -   a second container comprising an agent (a″), the agent        comprising (a″):        (a2) at least one color-imparting compound comprising at least        one effect pigment comprising α) a substrate platelet and β) a        coating, wherein the coating comprises at least one layer        prepared wet-chemically using a metal alkoxide and an        organosilicon compound having a basic group,    -   a third container comprises an agent (b), wherein the agent        comprises (b):

(b1) at least one sealing reagent.

DETAILED DESCRIPTION

The following detailed description is merely exemplary in nature and isnot intended to limit the disclosure or the application and uses of thesubject matter as described herein. Furthermore, there is no intentionto be bound by any theory presented in the preceding background or thefollowing detailed description.

Hair with a metallic finish or metallic highlights are in trend. Themetallic tone makes the hair look thicker and shinier.

There is a need to provide hair dyes with effect pigments that on theone hand have high wash and rub fastness and on the other hand do notnegatively affect hair properties such as manageability and feel. Forthis purpose, it would be desirable if the effect pigments used had ahigh covering power and could be applied to the hair in thin layers.

Accordingly, the task of the present disclosure was to provide acoloring system with effect pigments that has fastness propertiescomparable to oxidative coloring. Wash fastness properties should beoutstanding, but the use of oxidation dye precursors normally used forthis purpose should be avoided.

Surprisingly, it has now been found that the task can be excellentlysolved if keratinous materials, in particular human hair, are colored bya process in which at least two agents (a) and (b) are applied to thekeratinous materials (hair). Here, the first agent (a) comprises atleast one organic silicon compound from the group of silanes with one,two or three silicon atoms, and further at least one selected coloringcompound. In the agent (a), the organic silicon compound and thecolorant compound are thus prepared together. The second agent (b)comprises at least one sealing reagent.

When the two agents (a) and (b) were used in a dyeing process,keratinous material could be dyed with particularly high color intensityand high fastness properties.

A first object of the present disclosure is a method for coloringkeratinous material, in particular human hair, comprising the followingsteps:

-   -   Application of an agent (a) to the keratinous material, wherein        the agent (a) comprises:        (a1) at least one organic silicon compound selected from the        group of silanes having one, two or three silicon atoms, and        (a2) at least one color-imparting compound comprising at least        one effect pigment comprising α) a substrate platelet and β) a        coating,        wherein the coating comprises at least one layer wet-chemically        prepared using a metal alkoxide and an organosilicon compound        having a basic group, and

Application of an agent (b) to the keratinous material, wherein theagent (b) comprises:

(b1) at least one sealing reagent.

In the work leading to the present disclosure, it has been found thatthe preferential successive application of agents (a) and (b) enablesthe production of very stable and washfast colorations on the keratinousmaterials. Without being limited to this theory, it is suspected in thiscontext that the joint application of organic silicon compound (a1) andcolor-imparting compound (a2) leads to the formation of a particularlyresistant first film on the keratinous material. The first layer issealed with the application of the second agent (b). For example, afilm-forming polymer is now deposited on this first layer as a sealingreagent (b1) in the form of a further film.

Due to this special type of packaging—i.e., the joint application ofsilane (a1) and color-imparting compound (a2) and separate applicationof the sealing reagent (b1)—the film system produced in this wayexhibited improved resistance to external influences. In this way, thecolorant compounds (a2) were permanently fixed to the keratinousmaterial, so that extremely washfast colorations with good resistance toshampooing could be obtained.

The special coating of the effect pigment significantly increases theaffinity of the effect pigment for the first film (a1) formed by theorganic silicon compounds and the keratinous material.

Keratinous Material

Keratinous material includes hair, skin, nails (such as fingernailsand/or toenails). Wool, furs and feathers also fall under the definitionof keratinous material.

Preferably, keratinous material is understood to be human hair, humanskin and human nails, especially fingernails and toenails. Keratinousmaterial is understood to be human hair.

Agents (a) and (b)

In the procedure as contemplated herein, agents (a) and (b) are appliedto the keratinous material, in particular human hair. The two agents (a)and (b) are different from each other.

In other words, a first object of the present disclosure is a method fortreating keratinous material, in particular human hair, comprising thefollowing steps:

Application of an agent (a) to the keratinous material, wherein theagent (a) comprises:(a1) at least one organic silicon compound selected from the group ofsilanes having one, two or three silicon atoms, and(a2) at least one color-imparting compound comprising at least oneeffect pigment comprising α) a substrate platelet and β) a coating,wherein the coating comprises at least one layer wet-chemically preparedusing a metal alkoxide and an organosilicon compound having a basicgroup, andApplication of an agent (b) to the keratinous material, wherein theagent (b) comprises:(b1) at least one sealing reagent.

Agent (a)

Preferably, the agent (a) comprises the ingredients (a1) and (a2)essential to the present disclosure in a cosmetic carrier, particularlypreferably in an aqueous or aqueous-alcoholic cosmetic carrier. Thiscosmetic carrier can be liquid, gel or cream. Pasty, solid or powderycosmetic carriers can also be used for the preparation of agent (a). Forhair treatment, in particular hair coloring, such carriers are, forexample, creams, emulsions, gels or also surfactant-comprising foamingsolutions, such as shampoos, foam aerosols, foam formulations or otherpreparations suitable for application to the hair.

Preferably, the cosmetic carrier comprises—based on its weight—at least2 wt. % of water. Further preferably, the water content is above about10 wt. %, still further preferably above about 20 wt. % and particularlypreferably above about 40 wt. %. The cosmetic carrier can also beaqueous-alcoholic. Aqueous/alcoholic solutions in the context of thepresent disclosure are aqueous solutions comprising about 2 to about 70wt. % of a C₁-C₄ alcohol, more particularly ethanol or isopropanol. Theagents as contemplated herein may additionally contain other organicsolvents, such as methoxybutanol, benzyl alcohol, ethyl diglycol or1,2-propylene glycol. Preferred are all water-soluble organic solvents.

Organic Silicon Compounds from the Group of Silanes (a1)

As an ingredient (a1) essential to the present disclosure, the agent (a)comprises at least one organic silicon compound from the group ofsilanes having one, two or three silicon atoms.

Particularly preferably, the agent (a) comprises at least one organicsilicon compound (a1) selected from silanes having one, two or threesilicon atoms, the organic silicon compound comprising one or morehydroxyl groups and/or hydrolysable groups per molecule.

These organic silicon compounds (a1) or organic silanes included in theagent (a) is reactive compounds.

Organic silicon compounds, alternatively called organosilicon compounds,are compounds which either have a direct silicon-carbon bond (Si—C) orin which the carbon is bonded to the silicon atom via an oxygen,nitrogen or sulfur atom. The organic silicon compounds of the presentdisclosure are compounds comprising one to three silicon atoms. Organicsilicon compounds preferably contain one or two silicon atoms.

According to IUPAC rules, the term silane chemical compounds based on asilicon skeleton and hydrogen. In organic silanes, the hydrogen atomsare completely or partially replaced by organic groups such as(substituted) alkyl groups and/or alkoxy groups. In organic silanes,some of the hydrogen atoms may also be replaced by hydroxy groups.

In a particularly preferred embodiment, a method is exemplified by theapplication of an agent (a) to the keratinous material, said agent (a)comprising at least one organic silicon compound (a1) selected fromsilanes having one, two or three silicon atoms, said organic siliconcompound further comprising one or more hydroxyl groups or hydrolysablegroups per molecule.

In a very particularly preferred embodiment, a method is exemplified bythe application of an agent (a) to the keratinous material, said agent(a) comprising at least one organic silicon compound (a1) selected fromsilanes having one, two or three silicon atoms, said organic siliconcompound further comprising one or more basic chemical functions and oneor more hydroxyl groups or hydrolysable groups per molecule.

This basic group or basic chemical function can be, for example, anamino group, an alkylamino group, a dialkylamino group or atrialkylamino group, which is preferably connected to a silicon atom viaa linker. Preferably, the basic group is an amino group, a C₁-C₆alkylamino group or a Di(C₁-C₆)alkylamino group.

The hydrolysable group(s) is (are) preferably a C₁-C₆ alkoxy group,especially an ethoxy group or a methoxy group. It is preferred when thehydrolysable group is directly bonded to the silicon atom. For example,if the hydrolysable group is an ethoxy group, the organic siliconcompound preferably comprises a structural unit R′R″R′″Si—O—CH2-CH3. Theradicals R′, R″ and R′″ represent the three remaining free valences ofthe silicon atom.

A very particularly preferred method is wherein the agent (a) comprisesat least one organic silicon compound selected from silanes having one,two or three silicon atoms, the organic silicon compound preferablycomprising one or more basic chemical functions and one or more hydroxylgroups or hydrolysable groups per molecule.

Particularly satisfactory results were obtained when the agent (a)comprises at least one organic silicon (a1) compound of formula (I)and/or (II).

The compounds of formulas (I) and (II) are organic silicon compoundsselected from silanes having one, two or three silicon atoms, theorganic silicon compound comprising one or more hydroxyl groups and/orhydrolysable groups per molecule.

In another very particularly preferred embodiment, the method is whereinan agent is applied to the keratinous material (or human hair), theagent (a) comprising at least one organic silicon compound (a) offormula (I) and/or (II),

R₁R₂N-L-Si(OR₃)_(a)(R₄)_(b)  (I),

where

R₁, R₂ independently represent a hydrogen atom or a C₁-C₆ alkyl group,

-   -   L is a linear or branched bivalent C₁-C₂₀ alkylene group,

R₃ is a hydrogen atom or a C₁-C₆ alkyl group,

R₄ represents a C₁-C₆ alkyl group

-   -   a, represents an integer from 1 to 3, and    -   b stands for the integer 3−a,

(R₅O)_(c)(R₆)_(d)Si-(A)_(e)-[NR₇-(A′)]_(f)-[O-(A″)]_(g)-[NR₈-(A′″)]_(h)-Si(R₆′)_(d′)(OR₅′)_(c′)  (II),

where

-   -   R5, R5′, R5″ independently represent a hydrogen atom or a C₁-C₆        alkyl group,    -   R6, R6′ and R6″ independently represent a C₁-C₆ alkyl group,    -   A, A′, A″, A′″ and A″″ independently represent a linear or        divalent, bivalent C₁-C₂₀ alkylene group,    -   R₇ and R₈ independently represent a hydrogen atom, a C₁-C₆ alkyl        group, a hydroxy C₁-C₆ alkyl group, a C₂-C₆ alkenyl group, an        amino C₁-C₆ alkyl group or a group of formula (III)

-(A″″)-Si(R₆″)_(d)″(OR₅″)_(c)″  (III),

-   -   c, stands for an integer from 1 to 3,    -   d stands for the integer 3−c,    -   c′ stands for an integer from 1 to 3,    -   d′ stands for the integer 3−c′,    -   c″ stands for an integer from 1 to 3,    -   d″ stands for the integer 3-c″,    -   e stands for 0 or 1,    -   f stands for 0 or 1,    -   g stands for 0 or 1,    -   h stands for 0 or 1,    -   provided that at least one of the radicals e, f, g and h is        different from 0.

The substituents R₁, R₂, R₃, R₄, R₅, R₅′, R₅″, R₆, R₆′, R₆″, R₇, R₈, L,A, A′, A″, A′″ and A″″ in the compounds of formula (I) and (II) areexplained below as examples: Examples of a C₁-C₆ alkyl group are thegroups methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl and t-butyl,n-pentyl and n-hexyl. Propyl, ethyl and methyl are preferred alkylradicals. Examples of a C₂-C₆ alkenyl group are vinyl, allyl,but-2-enyl, but-3-enyl and isobutenyl, preferred C₂-C₆ alkenyl radicalsare vinyl and allyl. Preferred examples of a hydroxy C₁-C₆ alkyl groupare a hydroxymethyl, a 2-hydroxyethyl, a 2-hydroxypropyl, a3-hydroxypropyl, a 4-hydroxybutyl group, a 5-hydroxypentyl and a6-hydroxyhexyl group; a 2-hydroxyethyl group is particularly preferred.Examples of an amino C₁-C₆ alkyl group are the aminomethyl group, the2-aminoethyl group, the 3-aminopropyl group. The 2-aminoethyl group isparticularly preferred. Examples of a linear bivalent C₁-C₂₀ alkylenegroup include the methylene group (—CH₂—), the ethylene group(—CH₂—CH₂—), the propylene group (—CH₂—CH₂—CH₂—), and the butylene group(—CH₂—CH₂—CH₂—CH₂—). The propylene group (—CH₂—CH₂—CH₂—) is particularlypreferred. From a chain length of 3 C atoms, bivalent alkylene groupscan also be branched. Examples of branched divalent, bivalent C₃-C₂₀alkylene groups are (—CH₂—CH(CH₃)—) and (—CH₂—CH(CH₃)—CH₂—).

In the organic silicon compounds of the formula (I)

R₁R₂N-L-Si(OR₃)_(a)(R₄)_(b)  (I),

the radicals R₁ and R₂ independently of one another represent a hydrogenatom or a C₁-C₆ alkyl group. Very preferably, radicals R₁ and R₂ bothrepresent a hydrogen atom.

In the middle part of the organic silicon compound is the structuralunit or the linker -L- which stands for a linear or branched, divalentC₁-C₂₀ alkylene group.

A divalent C₁-C₂₀ alkylene group may alternatively be referred to as adivalent or divalent C₁-C₂₀ alkylene group, by which is meant that eachL grouping may form two bonds. One bond is from the amino group R₁R₂N tothe linker L, and the second bond is between the linker L and thesilicon atom.

Preferably, -L- represents a linear, divalent (i.e., divalent) C₁-C₂₀alkylene group. Further preferably -L- stands for a linear bivalentC₁-C₆ alkylene group. Particularly preferred -L stands for a methylenegroup (—CH₂—), an ethylene group (—CH₂—CH₂—), propylene group(—CH₂—CH₂—CH₂—) or butylene (—CH₂—CH₂—CH₂—CH₂—). L stands for apropylene group (—CH₂—CH₂—CH₂—)

The linear propylene group (—CH₂—CH₂—CH₂—) can alternatively be referredto as the propane-1,3-diyl group.

The organic silicon compounds of formula (I)

R₁R₂N-L-Si(OR₃)_(a)(R₄)_(b)  (I),

one end of each carries the silicon-comprising group—Si(OR₃)_(a)(R₄)_(b).

In the terminal structural unit —Si(OR₃)_(a)(R₄)_(b), R₃ is hydrogen orC₁-C₆ alkyl group, and R₄ is C₁-C₆ alkyl group. R₃ and R₄ independentlyof each other represent a methyl group or an ethyl group.

Here a stands for an integer from 1 to 3, and b stands for the integer3−a. If a stands for the number 3, then b is equal to 0. If a stands forthe number 2, then b is equal to 1. If a stands for the number 1, then bis equal to 2.

Particularly resistant films could be produced if the agent (a)comprises at least one organic silicon compound (a1) of formula (I) inwhich the radicals R₃, R₄ independently of one another represent amethyl group or an ethyl group.

When using the process for dyeing keratinous material, dyeings with thebest wash fastnesses could be obtained analogously when the agent (a)comprises at least one organic silicon compound of formula (I) in whichthe radicals R₃, R₄ independently of one another represent a methylgroup or an ethyl group.

Furthermore, dyeings with the best wash fastnesses could be obtained ifthe agent (a) comprises at least one organic silicon compound of theformula (I) in which the radical a represents the number 3. In this casethe radical b stands for the number 0.

In a further preferred embodiment, the agent (a) used in the process iswherein it comprises at least one organic silicon compound (a1) offormula (I), wherein

R₃, R₄ independently of one another represent a methyl group or an ethylgroup and

a stands for the number 3 and

b stands for the number 0.

In another preferred embodiment, a method is wherein the agent (a)comprises at least one organic silicon compound (a1) of formula (I),

R₁R₂N-L-Si(OR₃)_(a)(R₄)_(b)  (I),

where

R₁, R₂ both represent a hydrogen atom, and

L represents a linear, bivalent C₁-C₆-alkylene group, preferably apropylene group (—CH₂—CH₂—CH₂—) or an ethylene group (—CH₂—CH₂—),

R₃ represents a hydrogen atom, an ethyl group or a methyl group,

R₄ represents a methyl group or an ethyl group,

a stands for the number 3 and

b stands for the number 0.

Organic silicon compounds of the formula (I) which are particularlysuitable for solving the problem as contemplated herein are

In a further preferred embodiment, a method is wherein the agent (a)comprises at least one organic silicon compound (a1) selected from thegroup of

(3-Aminopropyl)triethoxysilane

(3-Aminopropyl)trimethoxysilane

1-(3-Aminopropyl)silantriol

(2-Aminoethyl)triethoxysilane

(2-Aminoethyl)trimethoxysilane

1-(2-Aminoethyl)silantriol

(3-Dimethylaminopropyl)triethoxysilane

(3-Dimethylaminopropyl)trimethoxysilane

1-(3-Dimethylaminopropyl)silantriol

(2-Dimethylaminoethyl)triethoxysilane.

(2-Dimethylaminoethyl)trimethoxysilane and/or

1-(2-dimethylaminoethyl)silanetriol.

The organic silicon compounds of formula (I) are commercially available.(3-aminopropyl)trimethoxysilane, for example, can be purchased fromSigma-Aldrich. Also (3-aminopropyl)triethoxysilane is commerciallyavailable from Sigma-Aldrich.

In a further embodiment, the agent comprises at least one organicsilicon compound (a1) of formula (II)

(R₅O)_(c)(R₆)_(d)Si-(A)_(e)-[NR₇-(A′)]_(f)-[O-(A″)]_(g)-[NR₈-(A″′)]_(h)-Si(R₆′)_(d′)(OR₅′)_(c)  (II).

The organosilicon compounds of formula (II) each bear at their two endsthe silicon-comprising groupings (R₅O)_(c)(R₆)_(d)Si— and—Si(R₆′)_(d′)(OR₅′)_(c′),

In the central part of the molecule of formula (II) there are the groups-(A)_(e)- and —[NR₇-(A′)]_(f)- and —[O-(A″)]_(g)- and —[NR₈-(A′″)]_(h)-.Here, each of the radicals e, f, g and h can independently of oneanother stand for the number 0 or 1, with the proviso that at least oneof the radicals e, f, g and h is different from 0. In other words, anorganic silicon compound of formula (II) comprises at least one groupingselected from the group of -(A)- and —[NR₇-(A′)]- and —[O-(A″)]- and—[NR₈-(A′″)]-.

In the two terminal structural units (R₅O)_(c)(R₆)_(d)Si— and—Si(R₆′)_(d′)(OR₅′)_(c′), the radicals R5, R5′, R5″ independently of oneanother represent a hydrogen atom or a C₁-C₆ alkyl group. The radicalsR6, R6′ and R6″ independently represent a C₁-C₆ alkyl group.

Here c stands for an integer from 1 to 3, and d stands for the integer3−c. If c stands for the number 3, then d is equal to 0. If c stands forthe number 2, then d is equal to 1. If c stands for the number 1, then dis equal to 2.

Analogously c′ stands for a whole number from 1 to 3, and d′ stands forthe whole number 3−c′. If c′ stands for the number 3, then d′ is 0. Ifc′ stands for the number 2, then d′ is 1. If c′ stands for the number 1,then d′ is 2.

Films with the highest stability or dyes with the best wash fastnessescould be obtained when the radicals c and c′ both stand for the number3. In this case d and d′ both stand for the number 0.

In another preferred embodiment, a method is wherein the agent (a)comprises at least one organic silicon compound (a1) of formula (II),

(R₅O)_(c)(R₆)_(d)Si-(A)_(e)-[NR₇-(A′)]_(f)-[O-(A″)]_(g)-[NR₈-(A′″)]_(h)-Si(R₆′)_(d′)(OR₅′)_(c′)  (II),

where

R5 and R5′ independently represent a methyl group or an ethyl group,

c and c′ both stand for the number 3 and

d and d′ both stand for the number 0.

If c and c′ are both the number 3 and d and d′ are both the number 0,the organic silicon compound of the present disclosure corresponds toformula (Ha)

(R₅O)₃Si-(A)_(e)-[NR₇-(A′)]_(f)-[O-(A″)]_(g)-[NR₈-(A′″)]_(h)-Si(OR₃)  (IIa).

The radicals e, f, g and h can independently stand for the number 0 or1, whereby at least one radical from e, f, g and h is different fromzero. The abbreviations e, f, g and h thus define which of the groupings-(A)_(e)- and —[NR₇-(A′)]_(f)- and —[O-(A″)]_(g)- and —[NR₈-(A′″)]_(h)-are in the middle part of the organic silicon compound of formula (II).

In this context, the presence of certain groupings has proved to beparticularly beneficial in terms of increasing washability. Particularlysatisfactory results were obtained when at least two of the radicals e,f, g and h stand for the number 1. Especially preferred e and f bothstand for the number 1. Furthermore, g and h both stand for the number0.

If e and f both stand for the number 1 and g and h both stand for thenumber 0, the organic silicon compound as contemplated hereincorresponds to formula (IIb)

(R₅O)_(c)(R₆)_(d)Si-(A)-[NR₇-(A′)]-Si(R₆′)_(d′)(OR₅′)_(c′)  (IIb).

The radicals A, A′, A″, A′″ and A″ independently represent a linear ordivalent, bivalent C₁-C₂₀ alkylene group. Preferably the radicals A, A′,A″, A′ and A″ independently of one another represent a linear, bivalentC₁-C₂₀ alkylene group. Further preferably the radicals A, A′, A″, A′ andA″ independently represent a linear bivalent C₁-C₆ alkylene group. Inparticular, the radicals A, A′, A″, A′ and A″ independently of oneanother represent a methylene group (—CH₂—), an ethylene group(—CH₂—CH₂—), a propylene group (—CH₂—CH₂—CH₂—) or a butylene group(—CH₂—CH₂—CH₂—CH₂—). Very preferably, the radicals A, A′, A″, A′″ andA″″ represent a propylene group (—CH₂—CH₂—CH₂—).

The divalent C₁-C₂₀ alkylene group may alternatively be referred to as adivalent or divalent C₁-C₂₀ alkylene group, by which is meant that eachgrouping A, A′, A″, A′″ and A″ may form two bonds.

The linear propylene group (—CH₂—CH₂—CH₂—) can alternatively be referredto as the propane-1,3-diyl group.

If the radical f represents the number 1, then the organic siliconcompound of formula (II) comprises a structural grouping —[NR₇-(A′)]-.

If the radical h represents the number 1, then the organic siliconcompound of formula (II) comprises a structural grouping —[NR₈-(A′″)]-.

Wherein radicals R₇ and R₈ independently represent a hydrogen atom, aC₁-C₆ alkyl group, a hydroxy-C₁-C₆ alkyl group, a C₂-C₆ alkenyl group,an amino-C₁-C₆ alkyl group or a group of the formula (III)

-(A″″)—Si(R₆″)_(d)″(OR₅″)_(c)″  (III).

Very preferably the radicals R₇ and R₈ independently of one anotherrepresent a hydrogen atom, a methyl group, a 2-hydroxyethyl group, a2-alkenyl group, a 2-aminoethyl group or a grouping of the formula(III).

If the radical f represents the number 1 and the radical h representsthe number 0, the organic silicon compound comprises the grouping[NR₇-(A′)] but not the grouping —[NR₈-(A′″)]. If the radical R₇ nowstands for a grouping of the formula (III), the agent (a) comprises anorganic silicon compound with 3 reactive silane groups.

In another preferred embodiment, a method is wherein the agent (a)comprises at least one organic silicon compound (a1) of formula (II),

(R₅O)_(c)(R₆)_(d)Si-(A)_(e)-[NR₇-(A′)]_(f)-[O-(A″)]_(g)-[NR₈-(A′″)]_(h)-Si(R₆′)_(d′)(OR₅′)_(c′)  (II),

where

e and f both stand for the number 1,

g and h both stand for the number 0,

A and A′ independently represent a linear, divalent C₁-C₆ alkylene groupand

R₇ represents a hydrogen atom, a methyl group, a 2-hydroxyethyl group, a2-alkenyl group, a 2-aminoethyl group or a group of formula (III).

In a further preferred embodiment, a method is wherein the agent (a)comprises at least one organic silicon compound of formula (II), wherein

e and f both stand for the number 1,

g and h both stand for the number 0,

A and A′ independently of one another represent a methylene group(—CH₂—), an ethylene group (—CH₂—CH₂—) or a propylene group(—CH₂—CH₂—CH₂), and

R₇ represents a hydrogen atom, a methyl group, a 2-hydroxyethyl group, a2-alkenyl group, a 2-aminoethyl group or a group of formula (III).

Organic silicon compounds of formula (II) which are well suited forsolving the problem as contemplated herein are:

3-(Trimethoxysilyl)-N-[3-(trimethoxysilyopropyl]-1-propanamine

The organic silicon compounds of formula (II) are commerciallyavailable. Bis(trimethoxysilylpropyl)amines with the CAS number82985-35-1 can be purchased from Sigma-Aldrich.

Bis[3-(triethoxysilyl)propyl]amines with the CAS number 13497-18-2 canbe purchased from Sigma-Aldrich, for example.N-methyl-3-(trimethoxysilyl)-N-[3-(trimethoxysilyl)propyl]-1-propanamineis alternatively referred to asBis(3-trimethoxysilylpropyl)-N-methylamine and can be purchasedcommercially from Sigma-Aldrich or Fluorochem.

3-(triethoxysilyl)-N,N-bis[3-(triethoxysilyl)propyl]-1-propanamine withthe CAS number 18784-74-2 can be purchased for example from Fluorochemor Sigma-Aldrich.

In a further preferred embodiment, a method is wherein the agent (a)comprises at least one organic silicon compound (a1) selected from thegroup of

3-(Trimethoxysilyl)-N-[3-(trimethoxysilyl)propyl]-1-propanamine

3-(Triethoxysilyl)-N-[3-(triethoxysilyl) propyl]-1-propanamine

N-Methyl-3-(trimethoxysilyl)-N-[3-(trimethoxysilyl)propyl]-1-propanamine

N-Methyl-3-(triethoxysilyl)-N-[3-(triethoxysilyl) propyl]-1-propanamine

2-[Bis[3-(trimethoxysilyl) propyl]amino]-ethanol

2-[Bis[3-(triethoxysilyl) propyl]amino]ethanol

3-(Trimethoxysilyl)-N,N-bis[3-(trimethoxysilyl) propyl]-1-propanamine

3-(Triethoxysilyl)-N,N-bis[3-(triethoxysilyl) propyl]-1-propanamine

N1,N1-Bis[3-(trimethoxysilyl) propyl]-1,2-ethanediamine,

N1,N1-Bis[3-(triethoxysilyl) propyl]-1,2-ethanediamine,

N,N-Bis[3-(trimethoxysilyl)propyl]-2-Propen-1-amine and/or

N,N-Bis[3-(triethoxysilyl)propyl]-2-propen-1-amine.

In further tests, in particular dyeing tests, it has also been found tobe particularly advantageous if the agent (a) applied to the keratinousmaterial in the process comprises at least one organic silicon compoundof the formula (IV)

R₉Si(OR₁₀)_(k)(R₁₁)_(m)  (IV).

The compounds of formula (IV) are organic silicon compounds selectedfrom silanes having one, two or three silicon atoms, the organic siliconcompound comprising one or more hydroxyl groups and/or hydrolysablegroups per molecule.

The organic silicon compound(s) of formula (IV) may also be called asilane of the alkyl-alkoxy-silane or alkyl-hydroxy-silane type,

R₉Si(OR₁₀)_(k)(R₁₁)_(m)  (IV),

where

R₉ stands for a C₁-C₁₈ alkyl group,

R₁₀ represents a hydrogen atom or a C₁-C₆ alkyl group,

R₁₁ represents a C₁-C₆ alkyl group

k is an integer from 1 to 3, and

m stands for the integer 3−k.

In a further preferred embodiment, the method is wherein the agent (a)comprises at least one organic silicon compound (a1) of formula (IV)

R₉Si(OR₁₀)_(k)(R₁₁)_(m)  (IV),

where

R₉ stands for a C₁-C₁₈ alkyl group,

R₁₀ represents a hydrogen atom or a C₁-C₆ alkyl group,

R₁₁ represents a C₁-C₆ alkyl group

k is an integer from 1 to 3, and

m stands for the integer 3−k.

In a further preferred embodiment, a process is wherein the agent (a)comprises, in addition to the organic silicon compound or compounds offormula (I), at least one further organic silicon compound of formula(IV)

R₉Si(OR₁₀)_(k)(R₁₁)_(m)  (IV),

where

R₉ stands for a C₁-C₁₈ alkyl group,

R₁₀ represents a hydrogen atom or a C₁-C₆ alkyl group,

R₁₁ represents a C₁-C₆ alkyl group

k is an integer from 1 to 3, and

m stands for the integer 3−k.

In a further preferred embodiment, a process is wherein the agent (a)comprises, in addition to the organic silicon compound or compounds offormula (II), at least one further organic silicon compound of formula(IV)

R₉Si(OR₁₀)_(k)(R₁₁)_(m)  (IV),

where

R₉ stands for a C₁-C₁₈ alkyl group,

R₁₀ represents a hydrogen atom or a C₁-C₆ alkyl group,

R₁₁ represents a C₁-C₆ alkyl group

k is an integer from 1 to 3, and

m stands for the integer 3−k.

In a further preferred embodiment, a process is wherein the agent (a)comprises, in addition to the organic silicon compound or compounds offormula (I) and/or (II), at least one further organic silicon compoundof formula (IV)

R₉Si(OR₁₀)_(k)(R₁₁)_(m)  (IV),

where

R₉ stands for a C₁-C₁₈ alkyl group,

R₁₀ represents a hydrogen atom or a C₁-C₆ alkyl group,

R₁₁ represents a C₁-C₆ alkyl group

k is an integer from 1 to 3, and

m stands for the integer 3−k.

In the organic silicon compounds of formula (IV), the radical R₉represents a C₁-C₁₈ alkyl group. This C₁-C₁₈ alkyl group is saturatedand can be linear or branched. Preferably, R₉ represents a linear C₁-C₁₈alkyl group. Preferably, R₉ represents a methyl group, an ethyl group,an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexylgroup, an n-octyl group, an n-dodecyl group or an n-octadecyl group.Particularly preferably, R₉ represents a methyl group, an ethyl group,an n-propyl group, an n-hexyl group or an n-octyl group.

In the organic silicon compounds of form (IV), the R₁₀ radicalrepresents a hydrogen atom or a C₁-C₆ alkyl group. Especiallypreferably, R₁₀ stands for a methyl group or an ethyl group.

In the organic silicon compounds of form (IV), the radical R₁₁represents a C₁-C₆ alkyl group. Particularly preferably, R₁₁ representsa methyl group or an ethyl group.

Furthermore, k stands for a whole number from 1 to 3, and m stands forthe whole number 3−k. If k stands for the number 3, then m is equal to0. If k stands for the number 2, then m is equal to 1. If k stands forthe number 1, then m is equal to 2.

Particularly stable films, i.e., dyeings with particularly good washfastness properties, could be obtained if an agent (a) comprising atleast one organic silicon compound (a1) corresponding to formula (IV):in which the radical k is the number 3, was used in the process. In thiscase the radical m stands for the number 0.

Organic silicon compounds of the formula (IV) which are particularlysuitable for solving the problem as contemplated herein are

In another preferred embodiment, a method is wherein the agent (a)comprises at least one organic silicon compound (a1) of formula (IV)selected from the group of

Methyltrimethoxysilane

Methyltriethoxysilane

Ethyltrimethoxysilane

Ethyltriethoxysilane

Propyltrimethoxysilane

Propyltriethoxysilane

Hexyltrimethoxysilane

Hexyltriethoxysilane

Octyltrimethoxysilane

Octyltriethoxysilane

Dodecyltrimethoxysilane

Dodecyltriethoxysilane.

Octyldecyltrimethoxysilane and/or

Octyldecyltriethoxysilane.

The organic silicon compounds described above are reactive compounds. Inthis context, it has been found preferable if the agent (a)comprises—based on the total weight of the agent (a)—one or more organicsilicon compounds (a1) in a total amount of about 0.1 to about 20 wt. %,preferably about 1 to about 15 wt. % and particularly preferably about 2to about 8 wt. %.

In a further preferred embodiment, a process is wherein the agent (a)comprises -based on the total weight of the agent (a)—one or moreorganic silicon compounds (a1) in a total amount of about 0.1 to about20 wt. %, preferably about 1 to about 15 wt. % and particularlypreferably about 2 to about 8 wt. %.

To achieve particularly good dyeing results, it is particularlyadvantageous to use the organic silicon compounds of the formula (I)and/or (II) in certain quantity ranges on agent (a). Particularlypreferably, the agent (a) comprises—based on the total weight of theagent (a)—one or more organic silicon compounds of the formula (I)and/or (II) in a total amount of about 0.1 to about 10 wt. %, preferablyabout 0.5 to about 5 wt. % and particularly preferably about 0.5 toabout 3 wt. %.

In a further preferred embodiment, a process is wherein the agent (a)comprises —based on the total weight of the agent (a)—one or moreorganic silicon compounds of the formula (I) and/or (II) in a totalamount of about 0.1 to about 10 wt. %, preferably about 0.5 to about 5wt. % and particularly preferably about 0.5 to about 3 wt. %.

Furthermore, it has proven to be particularly preferred if the organicsilicon compound(s) of formula (IV) is (are) also present in certainquantity ranges in agent (a). Particularly preferably, the agent (a)comprises—based on the total weight of the agent (a)—one or more organicsilicon compounds of the formula (IV) in a total amount of about 0.1 toabout 20 wt. %, preferably about 2 to about 15 wt. % and particularlypreferably about 4 to about 9 wt. %.

In a further preferred embodiment, a process is wherein the agent (a)comprises —based on the total weight of the agent (a)—one or moreorganic silicon compounds of the formula (IV) in a total amount of about0.1 to about 20 wt. %, preferably about 2 to about 15 wt. % andparticularly preferably about 3.2 to about 10 wt. %.

In the course of the work leading to this present disclosure, it wasfound that particularly stable and uniform films could be obtained onthe keratinous material even when the agent (a) included two organicsilicon compounds that were structurally different from each other.

In another preferred embodiment, a method is wherein the agent (a)comprises at least two structurally different organic silicon compounds.

In a preferred embodiment, a process is wherein an agent (a) comprisingat least one organic silicon compound of formula (I) and at least oneorganic silicon compound of formula (IV) is applied to the keratinousmaterial.

In an explicitly very particularly preferred embodiment, a process iswherein there is applied to the keratinous material an agent (a)comprising at least one organic silicon compound of formula (I) selectedfrom the group of (3-aminopropyl)triethoxysilane and(3-aminopropyl)trimethoxysilane and additionally comprising at least oneorganic silicon compound of formula (IV) selected from the group ofmethyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane,ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane,hexyltrimethoxysilane and hexyltriethoxysilane.

In a further preferred embodiment, a method is wherein the agent (a)comprises —based on the total weight of the agent (a):

about 0.5 to about 5 wt. % % of at least one first organic siliconcompound (a1) which is selected from the group of(3-aminopropyl)trimethoxysilane, (3-aminopropyl)triethoxysilane,(2-aminoethyl)trimethoxysilane, (2-aminoethyl)triethoxysilane,(3-dimethylaminopropyl)trimethoxysilane,(3-dimethylaminopropyl)triethoxysilane(2-dimethylaminoethyl)trimethoxysilane and(2-dimethylaminoethyl)triethoxysilane, and

about 3.2 to about 10 wt. % of at least one second organic siliconcompound (a1) selected from the group of methyltrimethoxysilane,methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane,propyltrimethoxysilane, propyltriethoxysilane, hexyltrimethoxysilane,hexyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane,dodecyltrimethoxysilane, dodecyltriethoxysilane,octadecyltrimethoxysilane and octadecyltriethoxysilane.

In this embodiment, the agent (a) comprises one or more organic siliconcompounds of a first group in a total amount of about 0.5 to about 3 wt.%. The organic silicon compounds of this first group are selected fromthe group of (3-aminopropyl)trimethoxysilane,(3-aminopropyl)triethoxysilane, (2-aminoethyl)trimethoxysilane,(2-aminoethyl)triethoxysilane, (3-dimethylaminopropyl)trimethoxysilane,(3-dimethylaminopropyl)triethoxysilane(2-dimethylaminoethyl)trimethoxysilane and/or(2-dimethylaminoethyl)triethoxysilane.

In this embodiment, the agent (a) comprises one or more organic siliconcompounds of a second group in a total amount of about 3.2 to about 10wt. %. The organic silicon compounds of this second group are selectedfrom the group of methyltrimethoxysilane, methyltriethoxysilane,ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane,propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane,octyltrimethoxysilane, octyltriethoxysilane, dodecyltrimethoxysilane,dodecyltriethoxysilane, octadecyltrimethoxysilane andoctadecyltriethoxysilane.

Even the addition of lesser amounts of water leads to hydrolysis inorganic silicon compounds with at least one hydrolysable group. Thehydrolysis products and/or organic silicon compounds having at least onehydroxy group may react with each other in a condensation reaction. Forthis reason, both the organosilicon compounds having at least onehydrolysable group and their hydrolysis and/or condensation products maybe present in the agent (a). When organosilicon compounds having atleast one hydroxyl group are used, both the organic silicon compoundshaving at least one hydroxyl group and their condensation products maybe present in the agent (a).

A condensation product is understood to be a product formed by thereaction of at least two organic silicon compounds each having at leastone hydroxyl group or hydrolysable group per molecule with eliminationof water and/or with elimination of an alkanol. The condensationproducts can be, for example, dimers, but also trimers or oligomers,with the condensation products being in equilibrium with the monomers.Depending on the amount of water used or consumed in the hydrolysis, theequilibrium shifts from monomeric organic silicon compounds tocondensation product.

Particularly satisfactory results were obtained when organic siliconcompounds of formula (I) and/or (II) were used in the process. Since, asalready described above, hydrolysis/condensation already starts attraces of moisture, the hydrolysis and/or condensation products of theorganic silicon compounds (I) and/or (II) are also included in thisembodiment.

Color-Forming Compounds (a2)

When agent (a) is applied to the keratinous material, the organicsilicon compound(s) (a1) comprising one or more hydroxyl groups orhydrolysable groups per molecule are first hydrolyzed and oligomerizedor polymerized in the presence of the water. The hydrolysis products oroligomers formed in this way have a particularly high affinity for thesurface of the keratinous material. The simultaneous presence of thecoloring compounds (a2) in the agent (a) integrates them into theresulting oligomers or polymers to form a colored film on the keratinousmaterial. Following the application of the agent (a), the agent (b). Thesuccessive application of agents (a) and (b) thus produces a colorationthat is particularly resistant to external influences. The colorantcompounds entrapped in these resistant films exhibit good wash fastness.

As an essential component (a2) of the present disclosure, the agent (a)used in the dyeing process therefore comprises at least onecolor-imparting compound. The at least one colorant compound (a2)comprises at least one effect pigment comprising α) a substrate plateletand β) a coating,

wherein the coating comprises at least one layer which has beenwet-chemically prepared using a metal alkoxide and an organosiliconcompound having a basic group.

Due to the coating as contemplated herein, the effect pigments show aparticularly high affinity to the keratinous material to be colored andto the film formed on the keratinous material with the aid of theorganic silicon compound(s) (a1).

Accordingly, with the aid of the effect pigments coated as contemplatedherein, keratinous fibers can be colored particularly intensively andpermanently.

The effect pigment has a substrate platelet.

The substrate wafer preferably has an average thickness of at most about150 nm, preferably less than about 50 nm, more preferably less thanabout 30 nm, particularly preferably at most about 25 nm, for example atmost about 20 nm. The average thickness of the substrate platelets is atleast about 1 nm, preferably at least about 2.5 nm, particularlypreferably at least about 5 nm, for example at least about 10 nm.Preferred ranges for substrate wafer thickness are about 2.5 to about 50nm, about 5 to about 50 nm, about 10 to about 50 nm; about 2.5 to about30 nm, about 5 to about 30 nm, about 10 to about 30 nm; about 2.5 toabout 25 nm, about 5 to about 25 nm, about 10 to about 25 nm, about 2.5to about 20 nm, about 5 to about 20 nm, and about 10 to about 20 nm.Preferably, each substrate plate has a thickness that is as uniform aspossible.

The substrate plate is preferably monolithic. Monolithic in this contextmeans comprising a single self-included unit without fractures,stratifications or inclusions, although microstructural changes mayoccur within the substrate platelet. The substrate platelet ispreferably homogeneous in structure, i.e., no concentration gradientoccurs within the platelet. In particular, the substrate platelet is notlayered and does not have particles or particulates distributed therein.

The size of the substrate platelet can be tailored to the specificapplication, for example the desired effect on a keratinous material.Typically, the substrate platelets have an average largest diameter ofabout 2 to about 200 μm, especially about 5 to about 100 μm.

In a preferred embodiment, the shape factor (aspect ratio), expressed bythe ratio of the average size to the average thickness, is at leastabout 80, preferably at least about 200, more preferably at least about500, particularly preferably more than about 750. The average size ofthe uncoated substrate platelets is the d50 value of the uncoatedsubstrate platelets. Unless otherwise stated, the d50 value wasdetermined using a Sympatec Helos device with quixel wet dispersion. Toprepare the sample, the sample to be analyzed was pre-dispersed inisopropanol for about 3 minutes.

The substrate platelet can be composed of any material that can beformed into platelet shape.

They can be of natural origin, but also synthetically produced.Materials from which the substrate platelets can be constructed includemetals and metal alloys, metal oxides, preferably aluminum oxide,inorganic compounds and minerals such as mica and (semi-)preciousstones, and plastics. Preferably, the substrate plates are constructedof a metal or alloy.

Any metal suitable for effect pigments can be used. Such metals includeiron and steel, as well as all air- and water-resistant (semi)metalssuch as platinum, tin, zinc, chromium, molybdenum and silicon, as wellas their alloys such as aluminum bronzes and brass. Preferred metals arealuminum, copper, silver and gold. Preferred substrate platelets includealuminum platelets and brass platelets, with aluminum substrateplatelets being particularly preferred.

Substrate plates made of aluminum can be produced, among other things,by punching out of aluminum foil or according to common milling andatomization techniques. For example, aluminum flakes are available fromthe Hall process, a wet milling process.

Other metal flakes, for example of bronze, can be obtained in a drygrinding process such as the Hametag process.

The substrate plates can have different shapes. For example, lamellar orlenticular metal platelets or so-called vacuum metallized pigments (VMP)can be used as substrate platelets. Lamellar substrate platelets areexemplified by an irregularly structured edge and are also referred toas “cornflakes” due to their appearance. Lenticular substrate flakeshave a regular round edge and are also known as “silver dollars” becauseof their appearance.

The metal or metal alloy substrate plates can be passivated, for exampleby anodizing (oxide layer) or chromating.

A coating can change the surface properties and/or optical properties ofthe effect pigment and increase the mechanical and chemical load-bearingcapacity of the effect pigments. For example, only the upper and/orlower side of the substrate wafer may be coated, with the side surfacesbeing recessed. Preferably, the entire surface of the optionallypassivated substrate platelets, including the side surfaces, is coveredby the layer. The substrate platelets are preferably completely encasedby the coating.

The coating may include one or more layers. In a preferred embodiment,the coating has only layer A. In a likewise preferred embodiment, thecoating has a total of at least two, preferably two or three, layers. Itmay be preferred to have the coating have two layers A and B, with layerB being different from layer A. Preferably, layer A is located betweenlayer B and the surface of the substrate plate. In yet another preferredembodiment, the coating has three layers A, B and C. In this embodiment,layer A is located between layer B and the surface of the substratewafer and layer C is located on top of layer B, which is different fromthe layer B below.

Suitable materials for the at least one layer, for example layers A, B,and C, are all substances that can be permanently applied to thesubstrate platelets. The materials should preferably be applicable infilm form. Preferably, the entire surface of the optionally passivatedsubstrate wafer, including the side surfaces, is enveloped by the atleast one layer, for example, layer A or layers A and B or layers A, Band C.

The at least one layer is prepared wet-chemically using a metal alkoxideand an organosilicon compound having a basic group.

It is essential to the present disclosure that an organosilicon compoundhaving a basic group is used in the preparation of the at least onelayer.

This basic group or basic chemical function can be, for example, anamino group, an alkylamino group, a dialkylamino group or atrialkylamino group, which is preferably connected to a silicon atom viaa linker. Preferably, the basic group is an amino group, a C₁-C₆alkylamino group or a Di(C₁-C₆)alkylamino group.

The organic silicon compound is preferably a silane with one, two orthree silicon atoms.

In a very particularly preferred embodiment, the wet chemicalpreparation of the at least one layer of the coating of the effectpigment employs an organosilicon compound having a basic group selectedfrom silanes having one, two or three silicon atoms, the organic siliconcompound further comprising one or more basic chemical groups and one ormore hydroxyl groups or hydrolysable groups per molecule.

Suitable organosilicon compounds with a basic group correspond to theorganosilicon compounds described above as suitable organic siliconcompounds (a1).

It is preferred that the organosilicon compound with a basic group hasthe formula (I) and/or (II),

R₁R₂N-L-Si(OR₃)_(a)(R₄)_(b)  (I),

where

R₁, R₂ independently represent a hydrogen atom or a C₁-C₆ alkyl group,

L is a linear or branched bivalent C₁-C₂₀ alkylene group,

R₃ is a hydrogen atom or a C₁-C₆ alkyl group,

R₄ represents a C₁-C₆ alkyl group

a, represents an integer from 1 to 3, and

b stands for the integer 3−a,

(R₅O)_(c)(R₆)_(d)Si-(A)_(e)-[NR₇-(A′)]_(f)-[O-(A″)]_(g)-[NR₈-(A′″)]_(h)-Si(R₆′)_(d′)(OR₅′)_(c′)  (II),

where

R5, R5′, R5″ independently represent a hydrogen atom or a C₁-C₆ alkylgroup,

R6, R6′ and R6″ independently represent a C₁-C₆ alkyl group,

A, A′, A″, A′″ and A″″ independently represent a linear or divalent,bivalent C₁-C₂₀ alkylene group,

R₇ and R₈ independently represent a hydrogen atom, a C₁-C₆ alkyl group,a hydroxy C₁-C₆ alkyl group, a C₂-C₆ alkenyl group, an amino C₁-C₆ alkylgroup or a group of formula (III)

-(A″″)—Si(R₆″)_(d)″(OR₅″)_(c)″  (III),

c, stands for an integer from 1 to 3,

d stands for the integer 3−c,

c′ stands for an integer from 1 to 3,

d′ stands for the integer 3−c′,

c″ stands for an integer from 1 to 3,

d″ stands for the integer 3-c″,

e stands for 0 or 1,

f stands for 0 or 1,

g stands for 0 or 1,

h stands for 0 or 1,

provided that at least one of the radicals e, f, g and h is differentfrom 0.

The organosilicon compound having a basic group is preferably selectedfrom the group of

(3-Aminopropyl)triethoxysilane

(3-Aminopropyl)trimethoxysilane

-1-(3-Aminopropyl)silantriol

(2-Aminoethyl)triethoxysilane

(2-Aminoethyl)trimethoxysilane

1-(2-Aminoethyl)silantriol

(3-Dimethylaminopropyl)triethoxysilane

(3-Dimethylaminopropyl)trimethoxysilane

-1-(3-Dimethylaminopropyl)silantriol

(2-Dimethylaminoethyl)triethoxysilane

(2-Dimethylaminoethyl)trimethoxysilane

1-(2-Dimethylaminoethyl)silantriol and

Mixtures of these.

Very preferably, (3-dimethylaminopropyl)triethoxysilane and/or(3-dimethylaminopropyl)trimethoxysilane are used as organosiliconcompounds with a basic group.

Even the addition of lesser amounts of water leads to hydrolysis inorganic silicon compounds with basic groups and with at least onehydrolysable group. The hydrolysis products and/or organic siliconcompounds with a basic group and with at least one hydroxy group and/orthe hydrolysis products of the metal alkoxides can react with each otherin a condensation reaction. For this reason, both the organosiliconcompounds with basic group and with at least one hydrolysable group andtheir hydrolysis and/or condensation products as well as thecondensation products with the hydrolysis products of the metalalkoxides and the condensation products of the hydrolysis products ofthe metal alkoxides can be included in the at least one layer.

A condensation product is understood to be either a product formed bythe reaction of at least two organic silicon compounds having a basicgroup and each having at least one hydroxyl group or hydrolysable groupper molecule with elimination of water and/or with elimination of analkanol. The condensation products can, for example, be dimers, or eventrimers or oligomers, where in the condensation products are always inbalance with the monomers. Depending on the amount of water used orconsumed in the hydrolysis, the equilibrium shifts from monomericorganic silicon compounds to condensation product.

A condensation product is also understood to mean a product that isformed by reacting at least one organic silicon compound having a basicgroup and having at least one hydroxyl group or hydrolysable groups permolecule with a hydrolysis product or a condensation product of themetal alkoxides with elimination of water and/or with elimination of analkanol.

The condensation products of the hydrolysis products of the metalalkoxides are usually metal oxides and/or metal oxide hydrates.

By using acids and/or bases, the hydrolysis and/or the condensationreaction can be influenced. For example, the formation of the at leastone layer can be influenced and controlled in terms of thickness, degreeof condensation of the condensation products, degree of cross-linking ofthe condensation products, reaction rate.

Accordingly, the at least one layer preferably comprises a metal oxideand/or metal oxide hydrate.

If the organic silicon compound having a basic group does not have ahydroxyl group or hydrolysable groups, the at least one layer comprisesthe organic silicon compound having a basic group in addition to a metaloxide and/or a metal oxide hydrate.

It is preferred that the metal oxide and/or metal oxide hydrate isselected from the group of silicon (di)oxide, silicon oxide hydrate,aluminum oxide, aluminum oxide hydrate, boron oxide, germanium oxide,manganese oxide, magnesium oxide, iron oxide, cobalt oxide, chromiumoxide, titanium dioxide, vanadium oxide, zirconium oxide, tin oxide,zinc oxide and mixtures thereof.

Layer A preferably has at least one low refractive index metal oxideand/or metal oxide hydrate. Preferably, layer A comprises at least about95 wt. % of low refractive index metal oxide (hydrate). Low refractiveindex materials have a refractive index of about 1.8 or less, preferablyabout 1.6 or less.

Low refractive index metal oxides suitable for Layer A include, forexample, silicon (di)oxide, silicon oxide hydrate, aluminum oxide,aluminum oxide hydrate, boron oxide, germanium oxide, manganese oxide,magnesium oxide, and mixtures thereof, with silicon dioxide beingpreferred. Layer A preferably has a thickness of about 1 to about 100nm, particularly preferably about 5 to about 50 nm, especiallypreferably about 5 to about 20 nm.

Layer B, if present, is different from Layer A and may contain at leastone highly refractive metal oxide. Highly refractive materials have arefractive index of at least about 1.9, preferably at least about 2.0,and more preferably at least about 2.4. Preferably, layer B comprises atleast about 95 wt. %, more preferably at least about 99 wt. %, of highrefractive index metal oxide(s).

If the layer B comprises a (highly refractive) metal oxide, itpreferably has a thickness of at least about 50 nm. Preferably, thethickness of layer B is no more than about 400 nm, more preferably nomore than about 300 nm.

Highly refractive metal oxides suitable for layer B are, for example,selectively light-absorbing (i.e., colored) metal oxides, such asiron(III) oxide (α- and γ-Fe2O3, red), cobalt(II) oxide (blue),chromium(III) oxide (green), titanium(III) oxide (blue, usually presentin admixture with titanium oxynitrides and titanium nitrides), andvanadium(V) oxide (orange), as well as mixtures thereof. Colorlesshigh-index oxides such as titanium dioxide and/or zirconium oxide arealso suitable.

Layer B can contain a selectively absorbing dye, preferably about 0.001to about 5 wt. %, particularly preferably about 0.01 to about 1 wt. %,in each case based on the total amount of layer B. Suitable dyes areorganic and inorganic dyes that can be stably incorporated into a metaloxide coating. Dyes in the sense of the present disclosure have asolubility in water (about 760 mmHg) at about 25° C. of more than about0.5 g/L and are therefore not to be regarded as pigments.

Alternatively, to a metal oxide, layer B may comprise a metal particlecarrier layer with metal particles deposited on the surface of the metalparticle carrier layer. In a preferred embodiment, the metal particlesdirectly cover a portion of the metal particle carrier layer. In thisembodiment, the effect pigment has areas in which there are no metalparticles, i.e., areas which are not covered with the metal particles.

The metal particle carrier layer comprises a metal layer and/or a metaloxide layer.

If the metal particle carrier layer comprises a metal layer and a metaloxide layer, the arrangement of these layers is not limited.

It is preferred that the metal particle support layer at least comprisesa metal layer. It is further preferred that the metal layer comprises anelement selected from tin (Sn), palladium (Pd), platinum (Pt) and gold(Au).

The metal layer can be formed, for example, by adding alkali to a metalsalt solution comprising the metal.

If the metal particle carrier layer comprises a metal oxide layer, thispreferably does not comprise silicon dioxide. The metal oxide layerpreferably comprises an oxide of at least one element selected from thegroup of Mg (magnesium), Sn (tin), Zn (zinc), Co (cobalt), Ni (nickel),Fe (iron), Zr (zirconium), Ti (titanium) and Ce (cerium). Particularlypreferably, the metal particle support layer iii) in the form of a metaloxide layer comprises a metal oxide of Sn, Zn, Ti and Ce.

The metal particle support layer in the form of a metal oxide layer canbe produced, for example, by hydrolysis of an alkoxide of a metalforming the metal of the metal oxide in a sol-gel process.

The thickness of the metal layer is preferably not more than about 30nm.

The metal particles may comprise at least one element selected from thegroup of aluminum (Al), titanium (Ti), chromium (Cr), iron (Fe), cobalt(Co), nickel (Ni), copper (Cu), zinc (Zn), ruthenium (Ru), rhodium (Rh),palladium (Pd), silver (Ag), tin (Sn), platinum (Pt), gold (Au), andalloys thereof. It is particularly preferred that the metal particlescomprise at least one element selected from copper (Cu), nickel (Ni) andsilver (Ag).

The average particle diameter of the metal particles is preferably notmore than 50 nm, more preferably not more than 30 nm. The distancebetween the metal particles is preferably not more than 10 nm.

Suitable methods for forming the metal particles include vacuumevaporation, sputtering, chemical vapor deposition (CVD), electrolessplating, or the like. Of these processes, electroless plating isparticularly preferred.

According to a preferred embodiment, the effect pigments have a furtherlayer C, comprising a metal oxide (hydrate), which is different from thelayer B underneath. Suitable metal oxides include silicon (di)oxide,silicon oxide hydrate, aluminum oxide, aluminum oxide hydrate, zincoxide, tin oxide, titanium dioxide, zirconium oxide, iron (III) oxide,and chromium (III) oxide. Silicon dioxide is preferred.

The layer C preferably has a thickness of about 10 to about 500 nm, morepreferably about 50 to about 300 nm.

The coating of the effect pigment has at least one layer that has beenwet-chemically prepared from a metal alkoxide and an organosiliconcompound having a basic group.

The at least one layer prepared using a metal alkoxide and anorganosilicon compound having a basic group may be layer A, B and/or C.In the case where the coating has only layer A, layer A has beenprepared using a metal alkoxide and an organosilicon compound having abasic group.

In the case where the coating of the effect pigment has two layers A andB, layer B has been prepared using a metal alkoxide and an organosiliconcompound having a basic group.

In the case where the coating has layers A, B and C, layer C has beenprepared using a metal alkoxide and an organosilicon compound having abasic group.

It is preferred that the effect pigment comprises a substrate plateletmade of aluminum and a layer A prepared using a silicon alkoxide and theorganosilicon compound having a basic group. Where the effect pigmentbased on a substrate platelet has a layer A and a layer C, it ispreferred that the effect pigment has a substrate platelet made ofaluminum, a layer A comprising silica, and a layer C, wherein a siliconalkoxide and the organosilicon compound having a basic group were usedto prepare the layer C.

The metal alkoxide used in the wet chemical coating process ispreferably a silicon alkoxide selected from the group of tetramethylorthosilicate, tetraethyl orthosilicate, tetraisopropyl orthosilicateand mixtures thereof, with tetraethyl orthosilicate being preferred.

Alternatively, aluminum alkoxides such as aluminum triisopropanolate oraluminum tri-sec-butanolate, zirconium alkoxides such as zirconiumpropylate, or titanium alkoxides such as titanium tetraethylate(tetraethyl orthotitanate) or titanium tetraisopropanolate(tetraisopropyl orthotitanate) can be used.

Alternatively, or in addition to a tetraalkoxysilane,alkyltrialkoxysilanes can be used in the wet chemical coating process toproduce the at least one layer, for example layer A or C.

Suitable alkyltrialkoxysilanes include, for example,methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane,ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane,hexyltrimethoxysilane, hexyltriethoxysilane, octyltrimethoxysilane,octyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane,octadecyltrimethoxysilane and/or octadecyltriethoxysilane.

Accordingly, the at least one layer may further comprise hydrolysisand/or condensation products of the alkyltrialkoxysilanes. Thecondensation products may include condensation products of two or morealkyltrialkoxysilanes, condensation products of alkyltrialkoxysilaneswith hydrolysis and/or condensation products of the organic siliconcompound having a basic group and having at least one hydroxyl group orhydrolysable groups per molecule, and/or condensation products ofalkyltrialkoxysilanes with hydrolysis and/or condensation products ofthe metal alkoxides.

If the organic silicon compound having a basic group does not have ahydroxyl group or hydrolysable groups, the at least one layer furthercomprises hydrolysis and/or condensation products of thealkyltrialkoxysilanes in addition to a metal oxide and/or a metal oxidehydrate and the organic silicon compound having a basic group.

In a preferred embodiment of the manufacturing process, the substratewafer used in step (a) has already been coated with at least one layerof a metal oxide and/or metal oxide hydrate.

An exemplary preparation method comprises dispersing the uncoatedsubstrate platelets or the substrate platelets already coated with layerA or with layers A and B and the organosilicon compound having at leastone basic group in a solution of a metal alkoxide such as tetraethylorthosilicate or aluminum triisopropanolate (usually in a solution oforganic solvent or a mixture of organic solvent and water with at leastabout 50 wt. % organic solvent such as a C₁ to C₄ alcohol), and adding aweak base or acid to hydrolyze the metal alkoxide, thereby forming afilm on the surface of the (coated) substrate platelets.

Layer B can be produced, for example, by hydrolytic decomposition of oneor more organic metal compounds and/or by precipitation of one or moredissolved metal salts, as well as any subsequent post-treatment (forexample, transfer of a formed hydroxide-comprising layer to the oxidelayers by annealing).

The wet chemical process is preferably a sol-gel process in which ametal alkoxide and an organosilicon compound with a basic group areused.

Although a mixture of two or more metal alkoxides can be used to producethe at least one layer, preferably layers A and/or C, only metalalkoxides of one metal, for example only silicon alkoxides or onlyaluminum alkoxides, are preferably used in each case to produce the atleast one layer.

It is preferred that the metal alkoxide used in the sol-gel process toproduce the at least one layer is selected from the group of tetramethylorthosilicate, tetraethyl orthosilicate, tetraisopropyl orthosilicate,and mixtures thereof, with tetraethyl orthosilicate being preferred.

It may be preferred that the at least one layer of the effect pigmentfurther comprises a color-imparting compound from the group of pigments.

Layers A and C serve as corrosion protection as well as chemical andphysical stabilization. Particularly preferably, layers A and C containsilicon dioxide or aluminum oxide applied by the sol-gel process.

The effect pigments based on coated substrate platelets preferably havea thickness of about 70 to about 500 nm, particularly preferably about100 to about 400 nm, especially preferably about 150 to about 320 nm,for example about 180 to about 290 nm. The low thickness of the coatedsubstrate platelets is achieved by keeping the thickness of the uncoatedsubstrate platelets low, but also by adjusting the thicknesses of thecoatings A and, if present, C to as small a value as possible.

The adhesion and abrasion resistance of effect pigments comprising α) asubstrate platelet and β) a coating, the coating having at least onelayer which has been prepared wet-chemically using a metal alkoxide andan organosilicon compound having a basic group, in the keratinousmaterial can be further increased by additionally modifying theoutermost layer, layer A, B or C depending on the structure, by organiccompound such as silanes, phosphoric acid esters, titanates, borates orcarboxylic acids. In this case, the organic compounds are bonded to thesurface of the outermost, preferably metal oxide-comprising, layer A, B,or C. The outermost layer denotes the layer that is spatially farthestfrom the substrate platelet. The organic compounds are preferablyfunctional silane compounds that can bind to the metal oxide-comprisinglayer A, B, or C. These can be either mono- or bifunctional compounds.Examples of bifunctional organic compounds aremethacryloxypropenyltrimethoxysilane,3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane,2-acryloxvethyltrimethoxysilane, 3-methacryloxy-propyltriethoxysilane,3-acry loxypropyltrimethoxysilane, 2-methacryloxyethyltriethoxysilane,2-acryloxyethyltriethoxysilane,3-methacryloxypropyltris(methoxyethoxy)silane,3-methacryloxypropyltris(butoxyethoxy)silane,3-methacryloxy-propyltris(propoxy)silane,3-methacryloxypropyltris(butoxy)silane,3-acryloxy-propyltris(methoxyethoxy)silane3-acryloxypropyltris(butoxyethoxy)silane,3-acryl-oxypropyltris(butoxy)silane, vinvltrimethoxysilane,vinyltriethoxysilane, vinylethyl dichlorosilane,vinylmethyldiacetoxysilane, vinylmethyldichlorosilane,vinylmethyldiethoxysilane, vinyltriacetoxysilane, vinyltrichlorosilane,phenylvinyldiethoxvsilane, or phenylallyldichlorosilane. Furthermore, amodification with a monofunctional silane, an alkyl silane or arylsilane, can be carried out. This has only one functional group that cancovalently bond to the surface of the effect pigment comprising α) asubstrate platelet and β) a coating, the coating having at least onelayer that has been wet-chemically prepared using a metal alkoxide andan organosilicon compound having a basic group, (i.e., to the outermostmetal oxide (hydrate)-comprising layer) or, if not completely covered,to the metal surface. The hydrocarbon residue of the silane points awayfrom the pigment. Depending on the type and nature of the hydrocarbonresidue of the silane, a varying degree of hydrophobicity of the pigmentis achieved. Examples of such silanes are hexadecyltrimethoxysilane,propyltrirnethoxysilane, etc. Particularly preferred are effect pigmentsbased on silica-coated aluminum substrate platelets surface-modifiedwith a monofunctional silane. Octyltrimethoxysilane,octyltriethoxysilane, hecadecyltrimethoxysilane andhecadecyltriethoxysiiane are particularly preferred. Due to the changedsurface properties/hydrophobization, an improvement can be achieved interms of adhesion, abrasion resistance and alignment in the application.

It has been shown that effect pigments with such a surface modificationalso exhibit better compatibility with the organosilicon compounds usedand/or their condensation or polymerization products.

Particularly satisfactory results could be obtained if the agent(a)—based on the total weight of the agent (a)—comprises one or moreeffect pigments in a total amount of about 0.01 to about 10 wt. %,preferably about 0.1 to about 8 wt. %, more preferably about 0.2 toabout 6 wt. % and very preferably about 0.5 to about 4.5 wt. %.

In addition to the effect pigment, the agent (a) may comprise furthercolorant compounds (a2) selected from the group of pigments and/ordirect dyes.

The use of pigments has proved to be particularly preferable in thiscontext.

In another very particularly preferred embodiment, a process is whereinthe agent (a) comprises at least one further colorant compound (a2) fromthe group of pigments.

Pigments within the meaning of the present disclosure are coloringcompounds which have a solubility in water at about 25° C. of less thanabout 0.5 g/L, preferably less than about 0.1 g/L, even more preferablyless than about 0.05 g/L. Water solubility can be determined, forexample, by the method described below: about 0.5 g of the pigment areweighed in a beaker. A stir-fish is added. Then one liter of distilledwater is added. This mixture is heated to about 25° C. for one hourwhile stirring on a magnetic stirrer. If undissolved components of thepigment are still visible in the mixture after this period, thesolubility of the pigment is below about 0.5 g/L. If the pigment-watermixture cannot be assessed visually due to the high intensity of thefinely dispersed pigment, the mixture is filtered. If a proportion ofundissolved pigments remains on the filter paper, the solubility of thepigment is below about 0.5 g/L.

Suitable pigments can be of inorganic and/or organic origin.

In a preferred embodiment, a process is wherein the agent (a) comprisesat least one further colorant compound (a2) from the group comprisinginorganic and/or organic pigments.

Preferred pigments are selected from synthetic or natural inorganicpigments. Inorganic pigments of natural origin can be produced, forexample, from chalk, ochre, umber, green earth, fired Terra di Siena orgraphite. Furthermore, black pigments such as iron oxide black, coloredpigments such as ultramarine or iron oxide red, and fluorescent orphosphorescent pigments can be used as inorganic pigments.

Particularly suitable are colored metal oxides, hydroxides and oxidehydrates, mixed-phase pigments, sulfur-containing silicates, silicates,metal sulfides, complex metal cyanides, metal sulphates, chromatesand/or molybdates. Particularly preferred pigments are black iron oxide(CI 77499), yellow iron oxide (CI 77492), red and brown iron oxide (CI77491), manganese violet (CI 77742), ultramarines (sodium aluminumsulfosilicates, CI 77007, Pigment Blue 29), chromium oxide hydrate(CI77289), iron blue (ferric ferrocyanide, CI77510) and/or carmine(cochineal).

Also particularly preferred pigments are colored pearlescent pigments.These are usually mica- and/or mica-based and can be coated with one ormore metal oxides. Mica belongs to the layer silicates. The mostimportant representatives of these silicates are muscovite, phlogopite,paragonite, biotite, lepidolite and margarite. To produce thepearlescent pigments in combination with metal oxides, the mica,muscovite or phlogopite, is coated with a metal oxide.

As an alternative to natural mica, synthetic mica coated with one ormore metal oxides can also be used as pearlescent pigment. Especiallypreferred pearlescent pigments are based on natural or synthetic mica(mica) and are coated with one or more of the metal oxides mentionedabove. The color of the respective pigments can be varied by varying thelayer thickness of the metal oxide(s).

Also preferred mica-based pigments are synthetically produced micaplatelets coated with metal oxide, based on synthetic fluorophlogopite(INCI: Synthetic Fluorphlogopite). The synthetic fluorophlogopiteplatelets are coated, for example, with tin oxide, iron oxide(s) and/ortitanium dioxide. The metal oxide layers can also have pigments such asiron hexacyanidoferrate(II/III) or carmine red Such mica pigments areavailable, for example, under the name SYNCRYSTAL from Eckart.

Accordingly, a preferred process is wherein the agent (a) comprises atleast one further colorant compound (a2) from the group of pigmentsselected from the group of colored metal oxides, metal hydroxides, metaloxide hydrates, silicates, metal sulfides, complex metal cyanides, metalsulfates, bronze pigments and/or from colored mica- or mica-basedpigments coated with at least one metal oxide and/or a metaloxychloride.

In a further preferred embodiment, the process is wherein the agent (a)comprises at least one further colorant compound (a2) from the group ofpigments selected from mica- or mica-based pigments which are reactedwith one or more metal oxides from the group comprising titanium dioxide(CI 77891), black iron oxide (CI 77499), yellow iron oxide (CI 77492),red and/or brown iron oxide (CI 77491, CI 77499), manganese violet (CI77742), ultramarine (sodium aluminum sulfosilicates, CI 77007, PigmentBlue 29), chromium oxide hydrate (CI 77289), chromium oxide (CI 77288)and/or iron blue (ferric ferrocyanide, CI 77510).

Other suitable pigments are based on metal oxide-coated platelet-shapedborosilicates. These are coated with tin oxide, iron oxide(s), silicondioxide and/or titanium dioxide, for example. Such borosilicate-basedpigments are available, for example, under the name MIRAGE from Eckartor Reflecks from BASF SE.

Examples of particularly suitable pigments are commercially availableunder the trade names Rona®, Colorona®, Xirona®, Dichrona® and Timiron®from Merck, Ariabel® and Unipure® from Sensient, Prestige® from EckartCosmetic Colors, Flamenco®, Cellini®, Cloisonne®, Duocrome®, Gemtone®,Timica®, MultiReflections, Chione from BASF SE and Sunshine® fromSunstar.

Very particularly preferred pigments with the trade name Colorona® are,for example:

Colorona Copper, Merck, MICA, CI 77491 (IRON OXIDES) Colorona PassionOrange, Merck, Mica, CI 77491 (Iron Oxides), Alumina Colorona PatinaSilver, Merck, MICA, CI 77499 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDE)Colorona RY, Merck, CI 77891 (TITANIUM DIOXIDE), MICA, CI 75470(CARMINE) Colorona Oriental Beige, Merck, MICA, CI 77891 (TITANIUMDIOXIDE), CI 77491 (IRON OXIDES) Colorona Dark Blue, Merck, MICA,TITANIUM DIOXIDE, FERRIC FERROCYANIDE Colorona Chameleon, Merck, CI77491 (IRON OXIDES), MICA Colorona Aborigine Amber, Merck, MICA, CI77499 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDE) Colorona BlackstarBlue, Merck, CI 77499 (IRON OXIDES), MICA Colorona Patagonian Purple,Merck, MICA, CI 77491 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDE), CI77510 (FERRIC FERROCYANIDE) Colorona Red Brown, Merck, MICA, CI 77491(IRON OXIDES), CI 77891 (TITANIUM DIOXIDE) Colorona Russet, Merck, CI77491 (TITANIUM DIOXIDE), MICA, CI 77891 (IRON OXIDES) Colorona ImperialRed, Merck, MICA, TITANIUM DIOXIDE (CI 77891), D&C RED NO. 30 (CI 73360)Colorona Majestic Green, Merck, CI 77891 (TITANIUM DIOXIDE), MICA, CI77288 (CHROMIUM OXIDE GREENS) Colorona Light Blue, Merck, MICA, TITANIUMDIOXIDE (CI 77891), FERRIC FERROCYANIDE (CI 77510) Colorona Red Gold,Merck, MICA, CI 77891 (TITANIUM DIOXIDE), CI 77491 (IRON OXIDES)Colorona Gold Plus MP 25, Merck, MICA, TITANIUM DIOXIDE (CI 77891), IRONOXIDES (CI 77491) Colorona Carmine Red, Merck, MICA, TITANIUM DIOXIDE,CARMINE Colorona Blackstar Green, Merck, MICA, CI 77499 (IRON OXIDES)Colorona Bordeaux, Merck, MICA, CI 77491 (IRON OXIDES) Colorona Bronze,Merck, MICA, CI 77491 (IRON OXIDES) Colorona Bronze Fine, Merck, MICA,CI 77491 (IRON OXIDES) Colorona Fine Gold MP 20, Merck, MICA, CI 77891(TITANIUM DIOXIDE), CI 77491 (IRON OXIDES) Colorona Sienna Fine, Merck,CI 77491 (IRON OXIDES), MICA Colorona Sienna, Merck, MICA, CI 77491(IRON OXIDES)

Colorona Precious Gold, Merck, Mica, CI 77891 (Titanium dioxide),Silica, CI 77491 (Iron oxides), Tin oxide

Colorona Sun Gold Sparkle MP 29, Merck, MICA, TITANIUM DIOXIDE, IRONOXIDES, MICA, CI 77891, CI 77491 (EU)

Colorona Mica Black, Merck, CI 77499 (Iron oxides), Mica, CI 77891(Titanium dioxide)Colorona Bright Gold, Merck, Mica, CI 77891 (Titanium dioxide), CI 77491(Iron oxides)

Colorona Blackstar Gold, Merck, MICA, CI 77499 (IRON OXIDES)

Colorona SynCopper, Merck, Synthetic Fluorphlogopite (and) Iron OxidesColorona SynBronze, Merck, Synthieic Fluorphlogopite (and) Iron Oxides

Further particularly preferred pigments with the trade name Xirona® are,for example:

Xirona Golden Sky, Merck, Silica, CI 77891 (Titanium Dioxide), Tin OxideXirona Caribbean Blue, Merck, Mica, CI 77891 (Titanium Dioxide), Silica,Tin Oxide Xirona Kiwi Rose, Merck, Silica, CI 77891 (Titanium Dioxide),Tin Oxide Xirona Magic Mauve, Merck, Silica, CI 77891 (TitaniumDioxide), Tin Oxide.

Xirona Le Rouge, Merck, Iron Oxides (and) Silica In addition,particularly preferred pigments with the trade name Unipure® are, forexample:

Unipure Red LC 381 EM, Sensient CI 77491 (Iron Oxides), Silica UnipureBlack LC 989 EM, Sensient, CI 77499 (Iron Oxides), Silica Unipure YellowLC 182 EM, Sensient, CI 77492 (Iron Oxides), Silica

Also particularly preferred pigments with the trade name Flamenco® are,for example:

Flamenco® Summit Turquoise T30D, BASF, Titanium Dioxide (and) MicaFlamenco® Super Violet 530Z, BASF, Mica (and) Titanium Dioxide

In a further embodiment, the agent (a) used in the process may alsocontain one or more colorant compounds (a2) from the group of organicpigments.

The organic pigments are correspondingly insoluble organic dyes orcolorants which may be selected, for example, from the group of nitroso,nitro-azo, xanthene, anthraquinone, isoindolinone, isoindoline,quinacridone, perinone, perylene, diketopyrrolopyorrole, indigo,thioindido, dioxazine and/or triarylmethane compounds.

Examples of particularly suitable organic pigments are carmine,quinacridone, phthalocyanine, sorghum, blue pigments with the ColorIndex numbers CI 42090, CI 69800, CI 69825, CI 73000, CI 74100, CI74160, yellow pigments with the Color Index numbers CI 11680, CI 11710,CI 15985, CI 19140, CI 20040, CI 21100, CI 21108, CI 47000, CI 47005,green pigments with the Color Index numbers CI 61565, CI 61570, CI74260, orange pigments with the Color Index numbers CI 11725, CI 15510,CI 45370, CI 71105, red pigments with the Color Index numbers CI 12085,CI 12120, CI 12370, CI 12420, CI 12490, CI 14700, CI 15525, CI 15580, CI15620, CI 15630, CI 15800, CI 15850, CI 15865, CI 15880, CI 17200, CI26100, CI 45380, CI 45410, CI 58000, CI 73360, CI 73915 and/or CI 75470.

In another particularly preferred embodiment, the process is wherein theagent (a) comprises at least one further coloring compound (a2) from thegroup of organic pigments selected from the group of carmine,quinacridone, phthalocyanine, sorghum, blue pigments having the colorindex numbers CI 42090, CI 69800, CI 69825, CI 73000, CI 74100, CI74160, yellow pigments having the color index numbers CI 11680, CI11710, CI 15985, CI 19140, CI 20040, CI 21100, CI 21108, CI 47000, CI47005, green pigments with Color Index numbers CI 61565, CI 61570, CI74260, orange pigments with Color Index numbers CI 11725, CI 15510, CI45370, CI 71105, red pigments with Color Index numbers CI 12085, CI12120, CI 12370, CI 12420, CI 12490, CI 14700, CI 15525, CI 15580, CI15620, CI 15630, CI 15800, CI 15850, CI 15865, CI 15880, CI 17200, CI26100, CI 45380, CI 45410, CI 58000, CI 73360, CI 73915, CI 75470 andmixtures thereof.

The organic pigment can also be a color paint. As contemplated herein,the term color lacquer means particles comprising a layer of absorbeddyes, the unit of particle and dye being insoluble under the abovementioned conditions. The particles can, for example, be inorganicsubstrates, which can be aluminum, silica, calcium borosilate, calciumaluminum borosilicate or even aluminum.

For example, alizarin color varnish can be used.

Other suitable colorants (a2) from the group of pigments are inorganicand/or organic pigments modified with a polymer. The polymermodification can, for example, increase the affinity of the pigments tothe respective material of the at least one layer.

Other effect pigments, such as metallic luster pigments, can also beused as a further coloring compound (a2).

The effect pigments may include, for example, pigments based on alamellar substrate platelet, pigments based on lenticular substrateplatelets, pigments based on substrate platelets comprising “vacuummetallized pigments” (VMP).

Suitable effect pigments include, for example, the pigments Alegrace®Marvelous, Alegrace© Gorgeous or Alegrace® Aurous from Schlenk MetallicPigments.

Also, suitable effect pigments are the aluminum-based pigments of theSILVERDREAM series and the pigments of the VISIONAIRE series fromEckart, which are based on aluminum or on copper/zinc-comprising metalalloys.

Other suitable effect pigments are based on metal oxide-coatedplatelet-shaped borosilicates. These are coated with tin oxide, ironoxide(s), silicon dioxide and/or titanium dioxide, for example. Suchborosilicate-based pigments are available, for example, under the nameMIRAGE from Eckart or Reflecks from BASF SE.

In a further embodiment of the process, the agent (a) may also compriseone or more colorant compounds selected from the group of organicpigments.

Due to their excellent light and temperature stability, the use of theabove pigments in agent (a) is particularly preferred. It is alsopreferred if the pigments used have a certain particle size. Thisparticle size leads on the one hand to an even distribution of thepigments in the formed polymer film and on the other hand avoids a roughhair or skin feeling after application of the cosmetic product. Ascontemplated herein, it is therefore advantageous if the at least onepigment has an average particle size D₅₀ of about 1 to about 50 μm,preferably about 5 to about 45 μm, preferably about 10 to about 40 μm,about 14 to about 30 μm. The mean particle size D₅₀, for example, can bedetermined using dynamic light scattering (DLS).

In a further preferred embodiment, the process is wherein the agent (a)comprises —based on the total weight of the agent (a)—one or morefurther colorant compound(s) (a2) in the form of pigments in a totalamount of from about 0.01 to about 10 wt. %, preferably from about 0.1to about 8 wt. %, more preferably from about 0.2 to about 6 wt. % andvery particularly preferably from about 0.5 to about 4.5 wt. %.

As further colorant compound(s) (a2), the agents (a) used in the processmay also contain one or more direct dyes. Direct-acting dyes are dyesthat draw directly onto the hair and do not require an oxidative processto form the color. Direct dyes are usually nitrophenylene diamines,nitroaminophenols, azo dyes, anthraquinones, triarylmethane dyes orindophenols.

The direct dyes within the meaning of the present disclosure have asolubility in water (about 760 mmHg) at about 25° C. of more than about0.5 g/L and are therefore not to be regarded as pigments.

Preferably, the direct dyes within the meaning of the present disclosurehave a solubility in water (about 760 mmHg) at about 25° C. of more thanabout 1 g/L.

Direct dyes can be divided into anionic, cationic and non-ionic directdyes.

In a further preferred embodiment, the process is wherein the agent (a)comprises at least one anionic, cationic and/or nonionic direct dye asfurther coloring compound (a2).

In a further preferred embodiment, the process is wherein the agent (a)comprises at least one further colorant compound (a2) from the groupcomprising anionic, nonionic, and/or cationic direct dyes.

Suitable cationic direct dyes include Basic Blue 7, Basic Blue 26, BasicViolet 2 and Basic Violet 14, Basic Yellow 57, Basic Red 76, Basic Blue16, Basic Blue 347 (Cationic Blue 347/Dystar), HC Blue No. 16, BasicBlue 99, Basic Brown 16, Basic Brown 17, Basic Yellow 57, Basic Yellow87, Basic Orange 31, Basic Red 51 Basic Red 76

As non-ionic direct dyes, non-ionic nitro and quinone dyes and neutralazo dyes can be used. Suitable non-ionic direct dyestuffs are thoselisted under the international designations or Trade names HC Yellow 2,HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, HC Orange 1,Disperse Orange 3, HC Red 1, HC Red 3, HC Red 10, HC Red 11, HC Red 13,HC Red BN, HC Blue 2, HC Blue 11, HC Blue 12, Disperse Blue 3, HC Violet1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9 knowncompounds, as well as 1,4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol,1,4-bis-(2-hydroxyethyl)-amino-2-nitrobenzene,3-nitro-4-(2-hydroxyethyl)-aminophenol2-(2-hydroxyethyl)amino-4,6-dinitrophenol,4-[(2-hydroxyethyl)amino]-3-nitro-1-methylbenzene,1-amino-4-(2-hydroxyethyl)-amino-5-chloro-2-nitrobenzene,4-amino-3-nitrophenol, 1-(2′-ureidoethyl)amino-4-nitrobenzene,2-[(4-amino-2-nitrophenyl)amino]benzoic acid,6-nitro-1,2,3,4-tetrahydroquinoxaline, 2-hydroxy-1,4-naphthoquinone,picramic acid and its salts, 2-amino-6-chloro-4-nitrophenol,4-ethylamino-3-nitrobenzoic acid and2-chloro-6-ethylamino-4-nitrophenol.

In the course of the work leading to the present disclosure, it has beenfound that dyeings of particularly high color intensity can be producedwith agents (a) comprising at least one anionic direct dye.

In an explicitly quite particularly preferred embodiment, the process istherefore wherein the agent (a) further comprises at least one anionicdirect dye as a further colorant compound (a2).

Anionic direct dyes are also called acid dyes. Acid dyes are direct dyesthat have at least one carboxylic acid group (—COOH) and/or onesulphonic acid group (—SO₃H). Depending on the pH value, the protonatedforms (—COOH, —SO₃H) of the carboxylic acid or sulphonic acid groups arein equilibrium with their deprotonated forms (—COO—, —SO₃ present). Theproportion of protonated forms increases with decreasing pH. If directdyes are used in the form of their salts, the carboxylic acid groups orsulphonic acid groups are present in deprotonated form and areneutralized with corresponding stoichiometric equivalents of cations tomaintain electro neutrality. The acid dyes can also be used in the formof their sodium salts and/or their potassium salts.

The acid dyes within the meaning of the present disclosure have asolubility in water (about 760 mmHg) at about 25° C. of more than about0.5 g/L and are therefore not to be regarded as pigments. Preferably theacid dyes within the meaning of the present disclosure have a solubilityin water (about 760 mmHg) at about 25° C. of more than about 1 g/L.

The alkaline earth salts (such as calcium salts and magnesium salts) oraluminum salts of acid dyes often have a lower solubility than thecorresponding alkali salts. If the solubility of these salts is belowabout 0.5 g/L (about 25° C., about 760 mmHg), they do not fall under thedefinition of a direct dye.

An essential characteristic of acid dyes is their ability to formanionic charges, whereby the carboxylic acid or sulphonic acid groupsresponsible for this are usually linked to different chromophoricsystems. Suitable chromophoric systems can be found, for example, in thestructures of nitrophenylenediamines, nitroaminophenols, azo dyes,anthraquinone dyes, triarylmethane dyes, xanthene dyes, rhodamine dyes,oxazine dyes and/or indophenol dyes.

In the context of one embodiment, a process for dyeing keratinousmaterial is thus preferred, which is wherein the agent (a) furthercomprises at least one anionic direct dye as further coloring compound(a2), which is selected from the group of the nitrophenylenediamines,the nitroaminophenols, the azo dyes, the anthraquinone dyes, thetriarylmethane dyes, the xanthene dyes, the rhodamine dyes, the oxazinedyes and/or the indophenol dyes, of the triarylmethane dyes, of thexanthene dyes, of the rhodamine dyes, of the oxazine dyes and/or of theindophenol dyes, the dyes from the abovementioned group each comprisingat least one carboxylic acid group (—COOH), a sodium carboxylate group(—COONa), a potassium carboxylate group (—COOK), a sulfonic acid group(—SO₃H), a sodium sulfonate group (—SO₃Na) and/or a potassium sulfonategroup (—SO₃K).

For example, one or more compounds from the following group can beselected as particularly well suited acid dyes: Acid Yellow 1 (D&CYellow 7, Citronin A, Ext. D&C Yellow No. 7, Japan Yellow 403, CI 10316,COLIPA no. B001), Acid Yellow 3 (COLIPA no.: C 54, D&C Yellow No. 10,Quinoline Yellow, E104, Food Yellow 13), Acid Yellow 9 (CI 13015), AcidYellow 17 (CI 18965), Acid Yellow 23 (COLIPA no. C. 29, Covacap Jaune W1100 (LCW), Sicovit Tartrazine 85 E 102 (BASF), Tartrazine, Food Yellow4, Japan Yellow 4, FD&C Yellow No. 5), Acid Yellow 36 (CI 13065), AcidYellow 121 (CI 18690), Acid Orange 6 (CI 14270), Acid Orange 7(2-Naphthol orange, Orange II, CI 15510, D&C Orange 4, COLIPA no.C.015), Acid Orange 10 (C.I. 16230; Orange G sodium salt), Acid Orange11 (CI 45370), Acid Orange 15 (CI 50120), Acid Orange 20 (CI 14600),Acid Orange 24 (BROWN 1; CI 20170; KATSU201; nosodiumsalt; Brown No.201; RESORCIN BROWN; ACID ORANGE 24; Japan Brown 201; D & C Brown No.1), Acid Red 14 (C.I. 14720), Acid Red 18 (E124, Red 18; CI 16255), AcidRed 27 (E 123, CI 16185, C-Rot 46, Real red D, FD&C Red Nr. 2, Food Red9, Naphthol red S), Acid Red 33 (Red 33, Fuchsia Red, D&C Red 33, CI17200), Acid Red 35 (CI C.I. 18065), Acid Red 51 (CI 45430, Pyrosin B,Tetraiodfluorescein, Eosin J, Iodeosin), Acid Red 52 (CI 45100, Food Red106, Solar Rhodamine B, Acid Rhodamine B, Red no. 106 Pontacyl BrilliantPink), Acid Red 73 (CI 27290), Acid Red 87 (Eosin, CI 45380), Acid Red92 (COLIPA no. C.53, CI 45410), Acid Red 95 (CI 45425, Erythtosine,Simacid Erythrosine Y), Acid Red 184 (CI 15685), Acid Red 195, AcidViolet 43 (Jarocol Violet 43, Ext. D&C Violet no. 2, C.I. 60730, COLIPAno. C.063), Acid Violet 49 (CI 42640), Acid Violet 50 (CI 50325), AcidBlue 1 (Patent Blue, CI 42045), Acid Blue 3 (Patent Blue V, CI 42051),Acid Blue 7 (CI 42080), Acid Blue 104 (CI 42735), Acid Blue 9 (E 133,Patent Blue AE, Amido blue AE, Erioglaucin A, CI 42090, C.I. Food Blue2), Acid Blue 62 (CI 62045), Acid Blue 74 (E 132, CI 73015), Acid Blue80 (CI 61585), Acid Green 3 (CI 42085, Foodgreen1), Acid Green 5 (CI42095), Acid Green 9 (C.I. 42100), Acid Green 22 (C.I. 42170), AcidGreen 25 (CI 61570, Japan Green 201, D&C Green No. 5), Acid Green 50(Brilliant Acid Green BS, C.I. 44090, Acid Brilliant Green BS, E 142),Acid Black 1 (Black no. 401, Naphthalene Black 10B, Amido Black 10B, CI20 470, COLIPA no. B15), Acid Black 52 (CI 15711), Food Yellow 8 (CI14270), Food Blue 5, D&C Yellow 8, D&C Green 5, D&C Orange 10, D&COrange 11, D&C Red 21, D&C Red 27, D&C Red 33, D&C Violet 2 and/or D&CBrown 1.

For example, the water solubility of anionic direct dyes can bedetermined in the following way. about 0.1 g of the anionic direct dyeis placed in a beaker. A stir-fish is added. Then add about 100 ml ofwater. This mixture is heated to about 25° C. on a magnetic stirrerwhile stirring. It is stirred for about 60 minutes. The aqueous mixtureis then visually assessed. If there are still undissolved radicals, theamount of water is increased—for example in steps of about 10 ml. Wateris added until the amount of dye used is completely dissolved. If thedye-water mixture cannot be assessed visually due to the high intensityof the dye, the mixture is filtered. If a proportion of undissolved dyesremains on the filter paper, the solubility test is repeated with ahigher quantity of water. If about 0.1 g of the anionic direct dyedissolves in about 100 ml water at about 25° C., the solubility of thedye is about 1 g/L.

Acid Yellow 1 is called 8-hydroxy-5,7-dinitro-2-naphthalenesulfonic aciddisodium salt and has a solubility in water of at least about 40 g/L(about 25° C.).

Acid Yellow 3 is a mixture of the sodium salts of mono- and disulfonicacids of 2-(2-quinolyl)-1H-indene-1,3(2H)-dione and has a watersolubility of about 20 g/L (about 25° C.).Acid Yellow 9 is the disodium salt of8-hydroxy-5,7-dinitro-2-naphthalenesulfonic acid, its solubility inwater is above about 40 g/L (about 25° C.).Acid Yellow 23 is the trisodium salt of4,5-dihydro-5-oxo-1-(4-sulfophenyl)-4-((4-sulfophenyl)azo)-1H-pyrazole-3-carboxylicacid and is highly soluble in water at 25° C.Acid Orange 7 is the sodium salt of 4-[(2-hydroxy-1-naphthyl)azo]benzenesulphonate. Its water solubility is more than about 7 g/L (about 25°C.).Acid Red 18 is the trisodium salt of7-hydroxy-8-[(E)-(4-sulfonato-1-naphthyl)-diazenyl)]-1,3-naphthalenedisulfonateand has an extremely high water solubility of more than 20 wt. %.Acid Red 33 is the disodium salt of5-amino-4-hydroxy-3-(phenylazo)-naphthalene-2,7-disulphonate, itssolubility in water is about 2.5 g/L (about 25° C.).Acid Red 92 is the disodium salt of3,4,5,6-tetrachloro-2-(1,4,5,8-tetrabromo-6-hydroxy-3-oxoxanthen-9-yl)benzoicacid, whose solubility in water is indicated as greater than about 10g/L (about 25° C.).Acid Blue 9 is the disodium salt of2-({4-[N-ethyl(3-sulfonatobenzyl]amino]phenyl}{4-[(N-ethyl(3-sulfonatobenzyl)imino]-2,5-cyclohexadien-1-ylidene}methyl)-benzenesulfonateand has a solubility in water of more than about 20 wt. % (about 25°C.).

A highly preferred process is therefore wherein the agent (a) comprisesat least one further colorant compound (a2) from the group of anionicdirect dyes selected from the group of Acid Yellow 1, acid yellow 3,acid yellow 9, acid yellow 17, acid yellow 23, acid yellow 36, acidyellow 121, acid orange 6, acid orange 7, acid orange 10, acid orange11, acid orange 15, acid orange 20, acid orange 24, acid red 14, acidred 27, acid red 33, acid red 35, Acid Red 51, Acid Red 52, Acid Red 73,Acid Red 87, Acid Red 92, Acid Red 95, Acid Red 184, Acid Red 195, AcidViolet 43, Acid Violet 49, Acid Violet 50, Acid Blue 1, Acid Blue 3,Acid Blue 7, Acid Blue 104, Acid Blue 9, Acid Blue 62, Acid Blue 74,Acid Blue 80, Acid Green 3, Acid Green 5, Acid Green 9, Acid Green 22,Acid Green 25, Acid Green 50, Acid Black 1, Acid Black 52, Food Yellow8, Food Blue 5, D&C Yellow 8, D&C Green 5, D&C Orange 10, D&C Orange 11,D&C Red 21, D&C Red 27, D&C Red 33, D&C Violet 2 and/or D&C Brown 1.

The direct dye(s), in particular the anionic direct dyes, can be used indifferent amounts in the agent (a) depending on the desired colorintensity. Particularly satisfactory results were obtained when theagent (a) comprises—based on its total weight—one or more direct dyes asa further coloring compound (a2) in a total amount of from about 0.01 toabout 10 wt. %, preferably from about 0.1 to about 8 wt. %, morepreferably from about 0.2 to about 6 wt. % and very particularlypreferably from about 0.5 to about 4.5 wt. %.

In a further preferred embodiment, the process is wherein the agent(a)—based on the total weight of the agent (a)—further comprises one ormore direct dyes as further colorant compound (a2) in a total amount offrom about 0.01 to about 10 wt. %, preferably from about 0.1 to about 8wt. %, more preferably from about 0.2 to about 6 wt. % and verypreferably from about 0.5 to about 4.5 wt. %.

Silicone Polymers (a3)

In another very particularly preferred embodiment, the agent (a) used inthe process additionally comprises at least one silicone polymer (a3).

Silicone polymers, which can alternatively be called silicones forshort, are understood to be poly(organo)siloxanes. Silicone polymers area group of synthetic polymers in which silicon atoms are linked viaoxygen atoms.

Silicone polymers are macromolecules with a molecular weight of at leastabout 500 g/mol, preferably at least about 1000 g/mol, more preferablyat least about 2500 g/mol, particularly preferably at least about 5000g/mol, which comprise repeating organic units.

The maximum molecular weight of the silicone polymer depends on thedegree of polymerization (number of polymerized monomers) and the batchsize and is partly determined by the polymerization method. For thepurposes of the present disclosure, it is preferred if the maximummolecular weight of the silicone polymer is not more than about 107g/mol, preferably not more than about 10⁶ g/mol, and particularlypreferably not more than about 105 g/mol.

The silicone polymers comprise many Si—O repeating units, and the Siatoms may carry organic radicals such as alkyl groups or substitutedalkyl groups.

Corresponding to the high molecular weight of silicone polymers, theseare based on more than about 10 Si—O repeat units, preferably more thanabout 50 Si—O repeat units, and more preferably more than about 100 Si—Orepeat units, most preferably more than about 500 Si—O repeat units.

The silicone polymers (a3) included in agent (a) are therefore differentfrom the silanes (a1) also included in agent (a).

In the context of one embodiment, a method for dyeing keratinousmaterial is thus preferred, which is wherein the agent comprises (a):

(a3) at least one silicone polymer.

In the work leading to the present disclosure, it was found thatincorporation of the silicone polymer (a3) into the agent (a) resultedin an improvement in hair feel.

The film produced by the oligomerization or polymerization of theorganosilicon compounds (silanes) (a1) may exhibit a certain stickinessor even softness, especially when higher amounts of silanes (a1) areused, which may have a detrimental effect on the feel of the keratinicmaterials on the one hand and on the durability of the film on theother. Without being committed to this theory, it is believed that thejoint application of the silane (a1) and the silicone polymer (a3) inthe agent (a) leads to a reaction or interaction of the two componentswith each other. When silane and silicone polymer are used together, thesilanes form a film, as previously described, into which the siliconepolymers are either incorporated, or to which the silicone polymersagglomerate. It has been found that the film formed in this way is muchmore supple, flexible, durable and less brittle.

Accordingly, it was observed that the rheological properties of the filmproduced by agent (a) could be improved by the addition of at least onesilicone polymer (a3). In the presence of the silicone polymers (a3),the film became firmer or more rigid, leaving the colored keratinousmaterials with a less sticky, smoother, and more pleasing appearance.Furthermore, the higher strength of the film also had positive effectson the fastness properties of the keratinic materials, especially ontheir rub fastness properties. Since the dyed films were more resistantwhen in contact with combs, brushes and textiles, they showed lessabrasion when in contact with these items.

When certain silicone polymers (a3) were used, the advantages describedabove were particularly pronounced. It has therefore been found to beparticularly preferred if the agents (a) used in the process contain atleast one alkoxy-modified silicone polymer and/or at least oneamino-modified silicone polymer (a3).

In the context of one embodiment, a method for dyeing keratinousmaterial is thus preferred, which is wherein the agent comprises (a):

(a3) at least one alkoxy-modified and/or amino-modified siliconepolymer.

In another preferred embodiment, a method is wherein the agent (a)comprises at least one alkoxy-modified silicone polymer.

Alkoxy-modified silicones are silicones whose structure includes atleast one structural alkoxy unit. This structural alkoxy unit can be,for example, an alkoxy group. Alkoxy groups are understood to be C₂-C₁₀alkoxy groups. The alkoxy group may be terminal to the silicone (i.e.,present, for example, as the group —O—CH₃ or as the group —O—CH₂—CH₃).However, it is equally as contemplated herein if the alkoxy group itselfstill carries a substituent; in this case, an alkoxy modification isunderstood to be at least one grouping located on the silicone such as,for example, (—CH2-CH2-O—), (—CH2-CH2-CH2-O—), (—CH(CH3)-CH2-O—),(—CH2-CH(CH3)-CH2-O—) or (—CH2-CH2-CH2-CH2-O—). Preferably, thealkoxy-modified silicones (A) carry at least one grouping (—CH2-CH2-O—)and/or (—CH2-CH2-CH2-O—).

The alkoxy groups may be linked to the silicone either via a carbon atomor via an oxygen atom, for example, the silicones may bear thestructural units of the formula (S-a), (S-b), (S-c) and/or (S-d):

It is particularly preferred if the alkoxy-modified silicone polymer(s)(a3) carry more than one alkoxy group, i.e., if the silicone polymers(a3) are poly alkoxylated. Polyalkoxylated silicones carry as structuralunits polyoxyalkylene groups, polyoxyethylene groups (i.e., groups ofthe type [—CH2-CH2-O—]_(m)) and/or poloxypropylene groups (i.e., groupsof the type [—CH(CH3)-CH2-O—]_(m) and/or [—CH2-CH2-CH2-O—]_(m)).Preferably, the number of polyoxyalkylene units in the silicone polymeris at least 2. Therefore, m is an integer greater than or equal to 2.

Particularly preferably, the alkoxy-modified silicone (a3) is a nonionicsilicone. Non-ionic silicones carry neither positive nor negativecharges.

Very particularly suitable polyalkoxylated silicones (a3) comprise atleast one structural unit of the formula (S-I)

whereinn is an integer from 2 to 20, preferably an integer from 4 to 18, morepreferably an integer from 6 to 16, still more preferably an integerfrom 8 to 14, and most preferably the number 12.

The positions marked with an asterisk * in the above formulas representthe free valences of the corresponding bonds, whereby the bond can be toa further Si atom, a further O atom and/or a further C atom.

In the context of one embodiment, a method for dyeing keratinousmaterial is thus preferred, which is wherein the agent comprises (a):

(a3) at least one silicone polymer comprising at least one structuralunit of formula (S-I)

whereinn is an integer from 2 to 20, preferably an integer from 4 to 18, morepreferably an integer from 6 to 16, still more preferably an integerfrom 8 to 14, and most preferably the number 12.

A preferred alkoxy-modified silicone polymer (a3) may contain, inaddition to one or more structural units of the general formula (S-I),further structural units that differ structurally from the units offormula (S-I). Particularly preferably, the alkoxy-modified siliconepolymer additionally comprises one or more dimethylsiloxane units.Depending on whether the silicone is linear or branched, it has two (inthe case of a chain linear silicone) or more (in the case of a branchedsilicone) end groups. It has been found to be particularly advantageousif a silicone polymer (a3) has a trimethylsilyloxy group (i.e., a group—O—Si(CH₃)₃) as end groups in each case.

In a further particularly preferred embodiment, the process is thereforewherein the agent (a) comprises at least one silicone polymer (a3) whichis composed of structural units of the formula (S-I), the formula(S-II), the formula (S-III) and the formula (S-IV),

wherein n—independently in each structural unit (S-I)—represents in eachcase an integer from 2 to 20, preferably an integer from 4 to 18, morepreferably an integer from 6 to 16, still more preferably an integerfrom 8 to 14, and most preferably the number 12.

A silicone polymer (a3) composed of structural units of the formula(S-I), the formula (S-II), the formula (S-III) and the formula (S-IV) isunderstood in this context to mean a silicone which exclusivelypossesses (in each case one or more) structural units of the formulae(S-I), (S-II), (S-III) and (S-IV). Here, the silicone can also containdifferent structural units of the formula (S-I), each of which isdistinguished by its number n.

The positions marked with an asterisk in the structural units eachrepresent the linkage points to the other structural units. For example,a very particularly preferred silicone polymer (a3) composed ofstructural units of formula (S-I), formula (S-II), formula (S-Ill) andformula (S-IV) may have the following structure:

x and y are chosen here depending on the desired molecular weight of thesilicone, and n represents one of the preferred or particularlypreferred integers described above as contemplated herein.

Both low molecular weight and higher molecular weight alkoxy-modifiedsilicones can be used as silicone polymers (a3). Particularly beneficialeffects were observed for silicone polymers (a3) with a molar mass ofabout 800 to about 10,000 g/mol, preferably of about 1,000 to about9,000 g/mol, further preferably of about 2,000 to about 8,000 g/mol andespecially preferably of about 2,500 to about 5,000 g/mol.

Particularly well-suited silicone polymers include:

Abil B 8843 from Evonik, PEG-14 DIMETHICONE

Xiameter OFX 0193 Fluid by the Company Dow Corning, PEG-12 Dimethicone

Furthermore, particularly satisfactory results were also obtained whenan agent (a) comprising an amino-modified silicone polymer (a3) was usedin the process. The amino-modified silicone polymer may alternatively bereferred to as an amino-functionalized silicone polymer or also as anamino silicone.

In another preferred embodiment, a method is wherein the agent (a)comprises at least one amino-modified silicone polymer.

Agent (a) may contain one or more different amino-modified siliconepolymers (a3). Such silicones can be exemplified, for example, by theformula (S-V)

M(R_(a)Q_(b)SiO_((4-a-b)/2)x)(R_(c)SiO_((4-c)/2)y)M  (S-V)

in which formula above R is a hydrocarbon or a hydrocarbon radicalhaving from 1 to about 6 carbon atoms, Q is a polar radical of thegeneral formula —R¹HZ wherein R¹ is a divalent linking group bonded tohydrogen and the radical Z composed of carbon and hydrogen atoms,carbon, hydrogen and oxygen atoms, or carbon, hydrogen and nitrogenatoms, and Z is an organic amino functional radical comprising at leastone amino functional group; “a” takes values ranging from about 0 toabout 2, “b” takes values ranging from about 1 to about 3, “a”+“b” isless than or equal to 3, and “c” is a number ranging from about 1 toabout 3, and x is a number ranging from 1 to about 2,000, preferablyfrom about 3 to about 50 and most preferably from about 3 to about 25,and y is a number in the range of from about 20 to about 10,000,preferably from about 125 to about 10,000 and most preferably from about150 to about 1,000, and M is a suitable silicone end group as known inthe prior art, preferably trimethylsiloxy. Non-limiting examples ofradicals represented by R include alkyl radicals, such as methyl, ethyl,propyl, isopropyl, isopropyl, butyl, isobutyl, amyl, isoamyl, hexyl,isohexyl and the like; alkenyl radicals, such as vinyl, halovinyl,alkylvinyl, allyl, haloallyl, alkylallyl; cycloalkyl radicals, such ascyclobutyl, cyclopentyl, cyclohexyl and the like; phenyl radicals,benzyl radicals, halohydrocarbon radicals, such as 3-chloropropyl,4-bromobutyl, 3,3,3-trifluoropropyl, chlorocyclohexyl, bromophenyl,chlorophenyl, and the like; and sulfur-comprising radicals, such asmercaptoethyl, mercaptopropyl, mercaptohexyl, mercaptophenyl, and thelike; preferably R is an alkyl radical comprising from 1 to about 6carbon atoms, and most preferably R is methyl. Examples of R¹ includemethylene, ethylene, propylene, hexamethylene, decamethylene,—CH₂CH(CH₃)CH₂—, phenylene, naphthylene, —CH₂CH₂SCH₂CH₂—, —CH₂CH₂OCH₂—,—OCH₂CH₂—, —OCH₂ CH₂CH₂—, —CH₂CH(CH₃)C(O)OCH₂—, —(CH₂)₃ CC(O)OCH₂CH₂—,—C₆H₄C₆H₄—, —C₆H₄CH₂C₆H₄—; and —(CH₂)₃C(O)SCH₂CH₂—.

Z is an organic amino functional residue comprising at least one aminofunctional group. One formula for Z is NH(CH₂)_(z)NH₂, where z is 1 ormore. Another formula for Z is —NH(CH₂)_(z)(CH₂)_(zz)NH, wherein both zand zz are independently 1 or more, this structure comprising diaminoring structures, such as piperazinyl. Z is most preferably an—NHCH₂CH₂NH₂ residue. Another formula for Z is —N(CH₂)_(z)(CH₂)_(zz)NX₂or —NX₂, wherein each X of X₂ is independently selected from the groupof hydrogen and alkyl groups having 1 to 12 carbon atoms, and zz is 0.

Q is most preferably a polar, amine-functional radical of the formula—CH₂CH₂CH₂NHCH₂CH₂NH₂. In the formulas, “a” takes values ranging fromabout 0 to about 2, “b” takes values ranging from about 2 to about 3,“a”+“b” is less than or equal to 3, and “c” is a number ranging fromabout 1 to about 3. The molar ratio of R_(a)Q_(b)SiO_((4-a-b)/2) unitsto R_(c)SiO_((4-c)y/2) units is in the range of about 1:2 to about 1:65,preferably from about 1:5 to about 1:65 and most preferably by about1:15 to about 1:20. If one or more silicones of the above formula areused, then the various variable substituents in the above formula may bedifferent for the various silicone components present in the siliconeblend.

In a particularly preferred embodiment, a method is exemplified by theapplication of an agent (a) to the keratinous material, wherein theagent (a) is an amino-modified silicone polymer (a3) of formula (S-VI)

R′_(a)G_(3-a)-Si(OSiG₂)_(n)-(OSiG_(b)R′_(2-b))_(m)—O-SiG_(3-a)-R′_(a)  (S-VI),

which means:

G is —H, a phenyl group, —OH, —O—CH₃, —CH₃, —O—CH₂CH₃, —CH₂CH₃,—O—CH₂CH₂CH₃, —CH₂CH₂CH₃, —O—CH(CH₃)₂, —CH(CH₃)₂, —O—CH₂CH₂CH₂CH₃,—CH₂CH₂CH₂CH₃, —O—CH₂CH(CH₃)₂, —CH₂CH(CH₃)₂, —O—CH(CH₃)CH₂CH₃,—CH(CH₃)CH₂CH₃, —O—C(CH₃)₃, —C(CH₃)₃;

a stands for a number between 0 and 3, especially 0;

b stands for a number between 0 and 1, especially 1,

m and n are numbers whose sum (m+n) is between 1 and 2000, preferablybetween 50 and 150, where n preferably assumes values from 0 to 1999 andfrom 49 to 149 and m preferably assumes values from 1 to 2000, from 1 to10,

R′ is a monovalent radical selected from

-   -   -Q-N(R″)—CH₂—CH₂—N(R″)₂    -   -Q-N(R″)₂    -   -Q-N+(R″)₃A⁻    -   -Q-N+H(R″)₂A⁻    -   -Q-N+H₂(R″)A⁻    -   -Q-N(R″)—CH₂—CH₂—N⁺R″H₂A⁻,        where each Q is a chemical bond, —CH₂—, —CH₂—CH₂—, —CH₂CH₂CH₂—,        —C(CH₃)₂—, —CH₂CH₂CH₂CH₂—, —CH₂C(CH₃)₂—, —CH(CH₃)CH₂CH₂—,        R″ represents identical or different radicals selected from the        group of —H, -phenyl, -benzyl, —CH₂—CH(CH₃)Ph, the C₁₋₂₀ alkyl        radicals, preferably —CH₃, —CH₂CH₃, —CH₂CH₂CH₃, —CH(CH₃)₂,        —CH₂CH₂CH₂H₃, —CH₂CH(CH₃)₂, —CH(CH₃)CH₂CH₃, —C(CH₃)₃, and A        represents an anion preferably selected from chloride, bromide,        iodide or methosulfate.

In another preferred embodiment, a method is exemplified by applying anagent (a) to the keratinous material, wherein the agent (a) comprises atleast one amino-modified silicone polymer (a3) of formula (S-VII),

wherein m and n are numbers whose sum (m+n) is between 1 and 2000,preferably between 50 and 150, n preferably assuming values from 0 to1999 and from 49 to 149, and m preferably assuming values from 1 to2000, from 1 to 10.

According to the INCI declaration, these silicones are calledtrimethylsilylamodimethicones.

In another preferred embodiment, a method is exemplified by theapplication of an agent (a) to the keratinous material, wherein theagent (a) comprises at least one amino-modified silicone polymer (a3) offormula (S-VIII)

in which R represents —OH, —O—CH₃ or a —CH₃ group and m, n1 and n2 arenumbers whose sum (m+n1+n2) is between 1 and 2000, preferably between 50and 150, the sum (n1+n2) preferably assuming values from 0 to 1999 andfrom 49 to 149 and m preferably assuming values from 1 to 2000, from 1to 10.

According to the INCI declaration, these amino-modified oramino-functionalized silicone polymers are known as amodimethicones.

Regardless of which amino-modified silicones are used, agents (a)comprising an amino-modified silicone polymer whose amine number isabove about 0.25 meq/g, preferably above about 0.3 meq/g and above about0.4 meq/g, are preferred. The amine number represents themilliequivalents of amine per gram of the amino-functional silicone. Itcan be determined by titration and expressed in the unit mg KOH/g.

In another preferred embodiment, a method is exemplified by applying anagent (a) to the keratinous material, wherein the agent (a) comprises atleast one amino-modified silicone polymer (a3) of the formula of formula(S-IX),

where

m and n mean numbers chosen so that the sum (n+m) is in the range 1 to1000,

n is a number in the range 0 to 999 and m is a number in the range 1 to1000,

R1, R2 and R3, which are the same or different, denote a hydroxy groupor a C1-4 alkoxy group,

wherein at least one of R1 to R3 represents a hydroxy group;

Other preferred methods are exemplified by the application of an agent(a) to the keratinous material, said agent (a) comprising at leastamino-functional silicone polymer of the formula of the formula (S-X)

in which

p and q mean numbers chosen so that the sum (p+q) is in the range 1 to1000,

p is a number in the range 0 to 999 and q is a number in the range 1 to1000,

R1 and R2, which are different, denote a hydroxy group or a C1-4 alkoxygroup, at least one of R1 to R2 denoting a hydroxy group.

The silicones of the formulas (S-IX) and (S-X) differ in the grouping atthe Si atom carrying the nitrogen-comprising group: In formula (S-IX),R2 represents a hydroxy group or a C1-4 alkoxy group, while the residuein formula (S-X) is a methyl group. The individual Si groupings, whichare marked with the indices m and n or p and q, do not have to bepresent as blocks; rather, the individual units can also be present in astatistically distributed manner, i.e. in the formulas (S-IX) and (S-X),not every R1-Si(CH₃)₂ group is necessarily bound to an —[O—Si(CH₃)₂]grouping.

Processes in which an agent (a) comprising at least one amino-modifiedsilicone polymer (a3) of the formula of the formula (S-XI) is applied tothe keratin fibers have also proved to be particularly effectiveregarding the desired effects

located in theA represents a group —OH, —O—Si(CH₃)₃, —O—Si(CH₃)₂OH, —O—Si(CH₃)₂OCH₃,D represents a group —H, —Si(CH₃)₃, —Si(CH₃)₂OH, —Si(CH₃)₂OCH₃,b, n and c stand for integers between 0 and 1000,with the specifications

-   -   n>0 and b+c>0    -   at least one of the conditions A=—OH or D=—H is fulfilled.

In the above formula (S-XI), the individual siloxane units arestatistically distributed with the indices b, c and n, i.e., they do notnecessarily have to be block copolymers.

Particularly beneficial effects regarding the improvement of rubfastness were observed when an agent (a) comprising a special4-morpholinomethyl-substituted silicone polymer (a3) was applied to thekeratinous material in the procedures. This very particularly preferredamino-functionalized silicone polymer comprises at least one structuralunit of the formula (S-XIII)

In the context of one embodiment, a method for dyeing keratinousmaterial is thus preferred, which is wherein the agent comprises (a):

(a3) at least one silicone polymer comprising at least one structuralunit of the formula (S-XIII)

Particularly beneficial effects in terms of improving rub fastness werealso observed when an agent (a) comprising a special4-morpholinomethyl-substituted silicone polymer (a3) was applied to thekeratinous material in the procedures. This very particularly preferredamino-functionalized silicone polymer comprises structural units of theformulae (S-XII) and of the formula (S-XIII)

In an explicitly quite particularly preferred embodiment, a method iswherein the agent (a) comprises at least one amino-modified siliconepolymer (a3) comprising structural units of the formula (S-XII) and ofthe formula (S-XIII)

Corresponding 4-morpholinomethyl-substituted silicone polymers aredescribed below.

A very particularly preferred amino-functionalized silicone polymer isknown as amodimethicone/morpholinomethyl silsesquioxane copolymer and iscommercially available in the form of the raw material Belsil ADM 8301 Efrom Wacker.

As a 4-morpholinomethyl-substituted silicone, for example, a siliconecan be used which has structural units of the formulae (S-XII),(S-XIII′) and (S-XIV′)

in whichR₁ is —CH₃, —OH, —OCH₃, —O—CH₂CH₃, —O—CH₂CH₂CH₃, or —O—CH(CH₃)₂; R₂ is—CH₃, —OH, or —OCH₃.

Particularly preferred agents (a) comprise at least one4-morpholinomethyl-substituted silicone of the formula (S-XV)

located in theR₁ is —CH₃, —OH, —OCH₃, —O—CH₂CH₃, —O—CH₂CH₂CH₃, or —O—CH(CH₃₂°)R₂ is —CH₃, —OH, or —OCH₃.B represents a group —OH, —O—Si(CH₃)₃, —O—Si(CH₃)₂OH, —O—Si(CH₃)₂OCH₃,D represents a group —H, —Si(CH₃)₃, —Si(CH₃)₂OH, —Si(CH₃)₂OCH₃,a, b and c stand independently for integers between 0 and 1000, with thecondition a +b+c>0m and n independently of each other stand for integers between 1 and1000

with the proviso that

-   -   at least one of the conditions B=—OH or D=—H is fulfilled,    -   the units a, b, c, m and n are distributed statistically or        blockwise in the molecule.

Structural formula (Si-VI) is intended to illustrate that the siloxanegroups n and m do not necessarily have to be directly bonded to aterminal grouping B or D, respectively. Rather, in preferred formulas(Si-VI) a>0 or b>0 and in particularly preferred formulas (Si-VI) a>0and c>0, i.e., the terminal grouping B or D is preferably attached to adimethylsiloxy grouping. Also, in formula (Si-VI), the siloxane units a,b, c, m and n are preferably statistically distributed.

The silicones used as contemplated herein represented by formula (Si-VI)can be trimethylsilyl-terminated (D or B=—Si(CH₃)₃), but they can alsobe dimethylsilylhydroxy-terminated on two sides ordimethylsilylhydroxy-terminated and dimethylsilylmethoxy-terminated onone side. Silicones particularly preferred in the context of the presentdisclosure are selected from silicones in which

B=—O—Si(CH₃)₂OH and D=—Si(CH₃)₃B=—O—Si(CH₃)₂OH and D=—Si(CH₃)₂OHB=—O—Si(CH₃)₂OH and D=—Si(CH₃)₂₀CH₃B=—O—Si(CH₃)₃ and D=—Si(CH₃)₂OHB=—O—Si(CH₃)₂₀CH₃ and D=—Si(CH₃)₂OHto everyone.

To produce particularly resistant films, the agent (a) comprises thesilicone polymer(s), in particular the alkoxy-modified and/or theamino-modified silicone polymers, preferably in specific ranges ofamounts.

Particularly flexible films of low tack were obtained when an agent (a)was used in the process which comprises—based on the total weight of theagent (a)—one or more silicone polymers (a3) in a total amount of fromabout 0.1 to about 8 wt. %, preferably from about 0.1 to about 5 wt. %,more preferably from about 0.1 to about 3 wt. % and very particularlypreferably from about 0.1 to about 0.5 wt. %.

In the context of a further preferred embodiment, a process is whereinthe agent (a) comprises—based on the total weight of the agent (a)—oneor more silicone polymers (a3) in a total amount of from about 0.1 toabout 15 wt. %, preferably from about 0.5 to about 12 wt. %, morepreferably from about 1 to about 10 wt. % and very particularlypreferably from about 2 to about 8 wt. %.

In an explicitly quite particularly preferred embodiment, a process iswherein the agent (a) comprises—based on the total weight of the agent(a)—one or more alkoxy-modified silicone polymers (a3) in a total amountof from about 0.1 to about 15 wt. %, preferably from about 0.5 to about12 wt. %, more preferably from about 1 to about 10 wt. % and veryparticularly preferably from about 2 to about 8 wt. %.

In the context of an explicitly quite particularly preferred embodiment,a process is wherein the agent (a) comprises—based on the total weightof the agent (a)—one or more amino-modified silicone polymers in a totalamount of from about 0.1 to about 15 wt. % preferably from about 0.5 toabout 12 wt. %, more preferably from about 1 to about 10 wt. % and veryparticularly preferably from about 2 to about 8 wt. %.

pH Value of the Agent (a)

It has been found preferable if the agent (a) is made up in the form ofa water-comprising agent adjusted to an alkaline pH.

To adjust the pH value, the agent (a) may contain at least onealkalizing agent.

To adjust the desired pH, the agents (a) may therefore also contain atleast one alkalizing agent. The pH values for the purposes of thepresent disclosure are pH values measured at a temperature of about 22°C.

As alkalizing agent, agent (a) may contain, for example, ammonia,alkanolamines and/or basic amino acids.

The alkanolamines that can the agent in the compositions are preferablyselected from primary amines having a C₂-C₆ alkyl parent carrying atleast one hydroxyl group. Preferred alkanolamines are selected from thegroup formed by 2-aminoethan-1-ol (monoethanolamine),3-aminopropan-1-ol, 4-aminobutan-1-ol, 5-aminopentan-1-ol,1-aminopropan-2-ol, 1-aminobutan-2-ol, 1-aminopentan-2-ol,1-aminopentan-3-ol, 1-aminopentan-4-ol, 3-amino-2-methylpropan-1-ol,1-amino-2-methylpropan-2-ol, 3-aminopropan-1,2-diol,2-amino-2-methylpropan-1,3-diol.

Particularly preferred alkanolamines are selected from 2-aminoethan-1-oland/or 2-amino-2-methylpropan-1-ol. A particularly preferred embodimentis therefore wherein the agent comprises, as alkalizing agent, analkanolamine selected from 2-aminoethan-1-ol and/or2-amino-2-methylpropan-1-ol.

For the purposes of the present disclosure, an amino acid is an organiccompound comprising in its structure at least one protonatable aminogroup and at least one —COOH or one —SO₃H group. Preferred amino acidsare aminocarboxylic acids, especially α-(alpha)-aminocarboxylic acidsand ω-aminocarboxylic acids, whereby α-aminocarboxylic acids areparticularly preferred.

Basic amino acids are those amino acids which have an isoelectric pointpI greater than about 7.

Basic α-aminocarboxylic acids contain at least one asymmetric carbonatom. In the context of the present disclosure, both enantiomers can beused equally as specific compounds or their mixtures, especially asracemates. However, it is particularly advantageous to use the naturallypreferred isomeric form, usually in L-configuration.

The basic amino acids are preferably selected from the group formed byarginine, lysine, ornithine and histidine, especially preferablyarginine and lysine. In a further particularly preferred embodiment, anagent is therefore wherein the alkalizing agent is a basic amino acidselected from the group of arginine, lysine, ornithine and/or histidine.

In addition, the product may contain other alkalizing agents, especiallyinorganic alkalizing agents. Inorganic alkalizing agents usable ascontemplated herein are preferably selected from the group formed bysodium hydroxide, potassium hydroxide, calcium hydroxide, bariumhydroxide, sodium phosphate, potassium phosphate, sodium silicate,sodium metasilicate, potassium silicate, sodium carbonate and potassiumcarbonate.

Particularly preferred alkalizing agents are ammonia, 2-aminoethan-1-ol(monoethanolamine), 3-aminopropan-1-ol, 4-aminobutan-1-ol,5-aminopentan-1-ol, 1-aminopropan-2-ol, 1-aminobutan-2-ol,1-aminopentan-2-ol, 1-aminopentan-3-ol, 1-aminopentan-4-ol,3-amino-2-methylpropan-1-ol, 1-Amino-2-methylpropan-2-ol,3-aminopropan-1,2-diol, 2-amino-2-methylpropan-1,3-diol, arginine,lysine, ornithine, histidine, sodium hydroxide, potassium hydroxide,calcium hydroxide, barium hydroxide, sodium phosphate, potassiumphosphate, sodium silicate, sodium metasilicate, potassium silicate,sodium carbonate and potassium carbonate.

Although the agents (a) are preferably adjusted to pH values in thealkaline range, it may nevertheless be necessary in principle to alsouse acidifiers in small quantities for fine adjustment of the desired pHvalue. Acidifiers suitable as contemplated herein are, for example,citric acid, lactic acid, acetic acid or also dilute mineral acids (suchas hydrochloric acid, sulfuric acid, phosphoric acid).

However, in the course of the work leading to the present disclosure, ithas been found that the presence of the alkalizing agent or theadjustment of the alkaline pH is essential for the formation ofresistant films on the keratinous material. The presence of excessiveamounts of acids can have a negative effect on the strength of thefilms. For this reason, it has proved preferable to keep the quantitiesof acids used in the agent (a) as low as possible. For this reason, itis advantageous if the total amount of organic and/or inorganic acidsincluded in the agent (a) does not exceed a certain value.

In a further preferred embodiment, a process is wherein the total amountof organic acids from the group comprising citric acid, tartaric acid,malic acid and lactic acid included in the agent (a) is below about 1wt. %, preferably below about 0.7 wt. %, more preferably below about 0.5wt. %, even more preferably below about 0.1 wt. % and most preferablybelow about 0.01 wt. %.

In a further preferred embodiment, a process is wherein the total amountof inorganic acids from the group comprising hydrochloric acid, sulfuricacid and phosphoric acid included in the agent (a) is below about 1 wt.%, preferably below about 0.7 wt. %, more preferably below about 0.5 wt.%, still more preferably below about 0.1 wt. % and very particularlypreferably below about 0.01 wt. %.

The maximum total amounts of the acids included in the agent (a) givenabove are always based on the total weight of the agent (a).

Agent (b)

The method of treatment of keratinous material includes, in addition tothe application of agent (a), the application of agent (b). The agent(b) used in the process is wherein it comprises at least one sealingreagent (b1).

The agent (b) is a post-treatment agent and the application of agent (b)to the keratinous material treated with agent (a) has the effect ofmaking the colorations obtained in the process more durable. Inparticular, the use of agent (b) can improve the fastness to washing andthe fastness to rubbing of the dyeings obtained in the process.

It is preferred that the sealing reagent (b1) comprises a compoundselected from the group of film-forming polymers, alkalizing agents,acidifying agents, and mixtures thereof.

It may be preferred that the sealing reagent (b1) comprises afilm-forming polymer.

Polymers are macromolecules with a molecular weight of at least about1000 g/mol, preferably of at least about 2500 g/mol, particularlypreferably of at least about 5000 g/mol, which include identical,repeating organic units. The polymers of the present disclosure may besynthetically produced polymers which are manufactured by polymerizationof one type of monomer or by polymerization of several types of monomerwhich are structurally different from each other. If the polymer isproduced by polymerizing a type of monomer, it is called a homo-polymer.If structurally different monomer types are used in polymerization, theresulting polymer is called a copolymer.

The maximum molecular weight of the polymer depends on the degree ofpolymerization (number of polymerized monomers) and the batch size andis determined by the polymerization method. In terms of the presentdisclosure, it is preferred if the maximum molecular weight of thefilm-forming hydrophobic polymer is not more than 107 g/mol, preferablynot more than about 10⁶ g/mol, and particularly preferably not more than105 g/mol.

As contemplated herein, a film-forming polymer is a polymer which canform a film on a substrate, for example on a keratinic material or akeratinic fiber. The formation of a film can be demonstrated, forexample, by viewing the polymer-treated keratinous material under amicroscope.

The film-forming polymers in agent (b) can be hydrophilic orhydrophobic.

In a first embodiment, it may be preferred to use at least onehydrophobic film-forming polymer as sealing reagent (b1) in agent (b).

A hydrophobic polymer is a polymer that has a solubility in water atabout 25° C. (about 760 mmHg) of less than about 1 wt. %.

The water solubility of the film-forming, hydrophobic polymer can bedetermined in the following way, for example. about 1 g of the polymeris placed in a beaker. Make up to about 100 g with water. A stir-fish isadded and the mixture is heated to about 25° C. on a magnetic stirrerwhile stirring. It is stirred for about 60 minutes. The aqueous mixtureis then visually assessed. If the polymer-water mixture cannot beassessed visually due to a high turbidity of the mixture, the mixture isfiltered. If a proportion of undissolved polymer remains on the filterpaper, the solubility of the polymer is less than about 1 wt. %.

These include acrylic acid-type polymers, polyurethanes, polyesters,polyamides, polyureas, cellulose polymers, nitrocellulose polymers,silicone polymers, acrylamide-type polymers and polyisoprenes.

Particularly well suited film-forming, hydrophobic polymers are, forexample, polymers from the group of copolymers of acrylic acid,copolymers of methacrylic acid, homopolymers or copolymers of acrylicacid esters, homopolymers or copolymers of methacrylic acid esters,homopolymers or copolymers of acrylic acid amides, homopolymers orcopolymers of methacrylic acid amides, copolymers of vinylpyrrolidone,copolymers of vinyl alcohol, copolymers of vinyl acetate, homopolymersor copolymers of ethylene, homopolymers or copolymers of propylene,homopolymers or copolymers of styrene, polyurethanes, polyesters and/orpolyamides.

In a further preferred embodiment, a process is wherein the agent (b)comprises at least one film-forming, hydrophobic polymer as sealingreagent (b1), which is selected from the group of the copolymers ofacrylic acid, the copolymers of methacrylic acid, the homopolymers orcopolymers of acrylic acid esters, the homopolymers or copolymers ofmethacrylic acid esters homopolymers or copolymers of acrylic acidamides, homopolymers or copolymers of methacrylic acid amides,copolymers of vinylpyrrolidone, copolymers of vinyl alcohol, copolymersof vinyl acetate, homopolymers or copolymers of ethylene, homopolymersor copolymers of propylene, homopolymers or copolymers of styrene,polyurethanes, polyesters and/or polyamides.

The film-forming hydrophobic polymers, which are selected from the groupof synthetic polymers, polymers obtainable by radical polymerization ornatural polymers, have proved to be particularly suitable for solvingthe problem as contemplated herein.

Other particularly well-suited film-forming hydrophobic polymers can beselected from the homopolymers or copolymers of olefins, such ascycloolefins, butadiene, isoprene or styrene, vinyl ethers, vinylamides, the esters or amides of (meth)acrylic acid having at least oneC₁-C₂₀ alkyl group, an aryl group or a C₂-C₁₀ hydroxyalkyl group.

Other film-forming hydrophobic polymers may be selected from the homo-or copolymers of isooctyl (meth)acrylate, isononyl (meth)acrylate,2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate), isopentyl(meth)acrylate, n-butyl (meth)acrylate), isobutyl (meth)acrylate, ethyl(meth)acrylate, methyl (meth)acrylate, tert-butyl (meth)acrylate,stearyl (meth)acrylate, hydroxyethyl (meth)acrylate, 2-hydroxypropyl(meth)acrylate, 3-hydroxypropyl (meth)acrylate and/or mixtures thereof.

Further film-forming hydrophobic polymers can be selected from the homo-or copolymers of (meth)acrylamide, N-alkyl(meth)acrylamides, those withC2-C18 alkyl groups, such as N-ethyl acrylamide, N-tert-butylacrylamide,le N-octylacrylamide, N-di(C1-C4)alkyl(meth)acrylamide.

Other preferred anionic copolymers are, for example, copolymers ofacrylic acid, methacrylic acid or their C₁-C₆ alkyl esters, as they aremarketed under the INCI Declaration Acrylates Copolymers. A suitablecommercial product is for example Aculyn® 33 from Rohm & Haas.Copolymers of acrylic acid, methacrylic acid or their C₁-C₆ alkyl estersand the esters of an ethylenically unsaturated acid and an alkoxylatedfatty alcohol are also preferred. Suitable ethylenically unsaturatedacids are especially acrylic acid, methacrylic acid and itaconic acid;suitable alkoxylated fatty alcohols are especially steareth-20 orceteth-20.

Very particularly preferred polymers on the market are, for example,Aculyn® 22 (Acrylates/Steareth-20 Methacrylate Copolymer), Aculyn® 28(Acrylates/Beheneth-25 Methacrylate Copolymer), Structure 2001@(Acryla-tes/Steareth-20 Itaconate Copolymer), Structure 3001@(Acrylates/Ceteth-20 Itaconate Copolymer), Structure Plus®(Acrylates/Aminoacrylates C10-30 Alkyl PEG-20 Itaconate Copolymer),Carbopol® 1342, 1382, Ultrez 20, Ultrez 21 (Acrylates/C10-30 AlkylAcrylate Crosspolymer), Synthalen W 2000® (Acrylates/Palmeth-25 AcrylateCopolymer) or the Rohme und Haas distributed Soltex OPT(Acrylates/C12-22 Alkyl methacrylate Copolymer).

Suitable polymers based on vinyl monomers may include, for example, thehomopolymers and copolymers of N-vinylpyrrolidone, vinylcaprolactam,vinyl-(C1-C6)alkyl-pyrrole, vinyl oxazole, vinyl thiazole, vinylpyrimidine or vinyl imidazole.

Also particularly suitable are the copolymersoctylacrylamide/acrylates/butylaminoethyl methacrylate copolymer, suchas those sold commercially by NATIONAL STARCH under the trade namesAMPHOMER® or LOVOCRYL® 47, or the copolymers ofacrylates/octylacrylamides sold under the trade names DERMACRYL® LT andDERMACRYL® 79 by NATIONAL STARCH.

Suitable olefin-based polymers include homopolymers and copolymers ofethylene, propylene, butene, isoprene and butadiene.

In another embodiment, the film-forming hydrophobic polymers may be theblock copolymers comprising at least one block of styrene or thederivatives of styrene. These block copolymers may be copolymerscomprising one or more blocks in addition to a styrene block, such asstyrene/ethylene, styrene/ethylene/butylene, styrene/butylene,styrene/isoprene, styrene/butadiene. Such polymers are commerciallydistributed by BASF under the trade name “Luvitol HSB”.

Surprisingly, it was found that particularly intense and washfastcolorations could be obtained when agent (b) included at least onefilm-forming polymer as sealing reagent (b1), which was selected fromthe group of homopolymers and copolymers of acrylic acid, homopolymersand copolymers of methacrylic acid, homopolymers and copolymers ofacrylic acid esters, homopolymers and copolymers of methacrylic acidesters, homopolymers and copolymers of acrylic acid amides, homopolymersand copolymers of methacrylic acid amides, homopolymers and copolymersof vinylpyrrolidone, homopolymers and copolymers of vinyl alcohol,homopolymers and copolymers of vinyl acetate, homopolymers andcopolymers of ethylene, homopolymers and copolymers of propylene,homopolymers and copolymers of styrene, polyurethanes, polyesters andpolyamides.

In a further preferred embodiment, a process is wherein the agent (b)comprises at least one film-forming polymer as sealing agent (b1), whichis selected from the group of the homopolymers and copolymers of acrylicacid, the homopolymers and copolymers of methacrylic acid, thehomopolymers and copolymers of acrylic acid esters, the homopolymers andcopolymers of methacrylic acid esters, homopolymers and copolymers ofacrylic acid amides, homopolymers and copolymers of methacrylic acidamides, homopolymers and copolymers of vinylpyrrolidone, homopolymersand copolymers of vinyl alcohol, homopolymers and copolymers of vinylacetate, homopolymers and copolymers of ethylene, homopolymers andcopolymers of propylene, homopolymers and copolymers of styrene,polyurethanes, polyesters and polyamides.

In a further embodiment, it may be preferred to use at least onehydrophilic film-forming polymer as sealing reagent (b1) in agent (b).

A hydrophilic polymer is a polymer that has a solubility in water atabout 25° C. (about 760 mmHg) of more than about 1 wt. %, preferablymore than about 2 wt. %.

The water solubility of the film-forming, hydrophilic polymer can bedetermined in the following way, for example. about 1 g of the polymeris placed in a beaker. Make up to about 100 g with water. A stir-fish isadded and the mixture is heated to about 25° C. on a magnetic stirrerwhile stirring. It is stirred for about 60 minutes. The aqueous mixtureis then visually assessed. A completely dissolved polymer appearsmacroscopically homogeneous. If the polymer-water mixture cannot beassessed visually due to a high turbidity of the mixture, the mixture isfiltered. If no undissolved polymer remains on the filter paper, thesolubility of the polymer is more than about 1 wt. %.

Nonionic, anionic and cationic polymers can be used as film-forming,hydrophilic polymers.

Suitable film-forming hydrophilic polymers may be selected, for example,from the group comprising polyvinylpyrrolidone (co)polymers, polyvinylalcohol (co)polymers, vinyl acetate (co)polymers, the carboxyvinyl(co)polymers, the acrylic acid (co)polymers, the methacrylic acid(co)polymers, the natural gums, the polysaccharides and/or theacrylamide (co)polymers.

Furthermore, it is particularly preferred to use polyvinylpyrrolidone(PVP) and/or a vinylpyrrolidone-comprising copolymer as film-forminghydrophilic polymer.

In another very particularly preferred embodiment, a process is whereinthe agent (b) comprises at least one film-forming, hydrophilic polymeras sealing reagent (b1), which is selected from the group ofpolyvinylpyrrolidone (PVP) and the copolymers of polyvinylpyrrolidone.

It is further preferred if the agent comprises polyvinylpyrrolidone(PVP) as the film-forming hydrophilic polymer. Surprisingly, the washfastness of the stains obtained with PVP-comprising agents (b) was alsoparticularly good.

Particularly well-suited polyvinylpyrrolidones are available, forexample, under the name Luviskol® K from BASF SE, especially Luviskol® K90 or Luviskol® K 85 from BASF SE.

The polymer PVP K30, which is marketed by Ashland (ISP, POI Chemical),can also be used as another explicitly very well suitedpolyvinylpyrrolidone (PVP). PVP K 30 is a polyvinylpyrrolidone which ishighly soluble in cold water and has the CAS number 9003-39-8. Themolecular weight of PVP K 30 is about 40000 g/mol.

Other particularly suitable polyvinylpyrrolidones are the substancesknown under the trade names LUVITEC K 17, LUVITEC K 30, LUVITEC K 60,LUVITEC K 80, LUVITEC K 85, LUVITEC K 90 and LUVITEC K 115 and availablefrom BASF.

The use of film-forming hydrophilic polymers as sealing reagent (b1)from the group of copolymers of polyvinylpyrrolidone also led toparticularly good and washfast color results. Vinylpyrrolidone-vinylester copolymers, such as those marketed under the trademark Luviskol®(BASF), are particularly suitable film-forming hydrophilic polymers.Luviskol® VA 64 and Luviskol® VA 73, both vinylpyrrolidone/vinyl acetatecopolymers, are particularly preferred non-ionic polymers.

Of the vinylpyrrolidone-comprising copolymers, a styrene/VP copolymerand/or a vinylpyrrolidone-vinyl acetate copolymer and/or a VP/DMAPAacrylates copolymer and/or a VP/vinyl caprolactam/DMAPA acrylatescopolymer are particularly preferred in cosmetic compositions.

Vinylpyrrolidone-vinyl acetate copolymers are marketed under the nameLuviskol® VA by BASF SE. For example, a VP/Vinyl Caprolactam/DMAPAAcrylates copolymer is sold under the trade name Aquaflex® SF-40 byAshland Inc. For example, a VP/DMAPA acrylates copolymer is marketed byAshland under the name Styleze CC-10 and is a highly preferredvinylpyrrolidone-comprising copolymer.

Other suitable copolymers of polyvinylpyrrolidone may also be thoseobtained by reacting N-vinylpyrrolidone with at least one furthermonomer from the group comprising V-vinylformamide, vinyl acetate,ethylene, propylene, acrylamide, vinylcaprolactam, vinylcaprolactoneand/or vinyl alcohol.

In another very particularly preferred embodiment, a process is whereinthe agent (b) comprises at least one film-forming, hydrophilic polymeras sealing reagent (b1), which is selected from the group ofpolyvinylpyrrolidone (PVP), vinylpyrrolidone/vinyl acetate copolymers,vinylpyrrolidone/styrene copolymers, vinylpyrrolidone/ethylenecopolymers, vinylpyrrolidone/propylene copolymers,vinylpyrrolidone/vinylcaprolactam copolymers,vinylpyrrolidone/vinylformamide copolymers and/or vinylpyrrolidone/vinylalcohol copolymers.

Another suitable copolymer of vinylpyrrolidone is the polymer knownunder the INCI designation maltodextrin/VP copolymer.

Furthermore, intensively colored keratinous material, especially hair,could be obtained with particularly good wash fastness properties when anonionic film-forming hydrophilic polymer was used as the film-forminghydrophilic polymer.

In another embodiment, the agent (b) may comprise at least one nonionic,film-forming, hydrophilic polymer as sealing reagent (b1).

As contemplated herein, a non-ionic polymer is understood to be apolymer which in a protic solvent—such as water—under standardconditions does not carry structural units with permanent cationic oranionic groups, which must be compensated by counterions whilemaintaining electron neutrality. Cationic groups include quaternizedammonium groups but not protonated amines. Anionic groups includecarboxylic and sulphonic acid groups.

Preference is given to products comprising, as a non-ionic,film-forming, hydrophilic polymer, at least one polymer selected fromthe group of

Polyvinylpyrrolidone,

Copolymers of N-vinylpyrrolidone and vinyl esters of carboxylic acidscomprising 2 to 18 carbon atoms of N-vinylpyrrolidone and vinyl acetate,

Copolymers of N-vinylpyrrolidone and N-vinylimidazole andmethacrylamide,

Copolymers of N-vinylpyrrolidone and N-vinylimidazole and acrylamide,

Copolymers of N-vinylpyrrolidone with N,N-di(C1 to C4)alkylamino-(C2 toC4)alkyl acrylamide.

If copolymers of N-vinylpyrrolidone and vinyl acetate are used, it isagain preferable if the molar ratio of the structural units included inthe monomer N-vinylpyrrolidone to the structural units of the polymerincluded in the monomer vinyl acetate is in the range from about 20:80to about 80:20, in particular from about 30:70 to about 60:40. Suitablecopolymers of vinyl pyrrolidone and vinyl acetate are available, forexample, under the trademarks Luviskol® VA 37, Luviskol® VA 55,Luviskol® VA 64 and Luviskol® VA 73 from BASF SE.

Another particularly preferred polymer is selected from the INCIdesignation VP/Methacrylamide/Vinyl Imidazole Copolymer, which isavailable under the trade name Luviset Clear from BASF SE.

Another particularly preferred nonionic, film-forming, hydrophilicpolymer is a copolymer of N-vinylpyrrolidone andN,N-dimethylaminiopropylmethacrylamide, which is sold, for example, byISP under the INCI designation VP/DMAPA Acrylates Copolymer, e.g., underthe trade name Styleze® CC 10.

A cationic polymer is the copolymer of N-vinylpyrrolidone,N-vinylcaprolactam, N-(3-dimethylaminopropyl)methacrylamide and3-(methacryloylamino)propyl-lauryl-dimethylammonium chloride (INCIdesignation: Polyquaternium-69), which is marketed, for example, underthe trade name AquaStyle® 300 (about 28 to about 32 wt. % activesubstance in ethanol-water mixture, molecular weight 350000) by ISP.

Other suitable film-forming, hydrophilic polymers include

Vinylpyrrolidone-vinylimidazolium methylchloride copolymers, as offeredunder the designations Luviquat© FC 370, FC 550 and the INCI designationPolyquaternium-16 as well as FC 905 and HM 552,

Vinylpyrrolidone-vinylcaprolactam-acrylate terpolymers, as they arecommercially available with acrylic acid esters and acrylic acid amidesas a third monomer component, for example under the name Aquaflex® SF40.

Polyquaternium-11 is the reaction product of diethyl sulphate with acopolymer of vinyl pyrrolidone and dimethylaminoethyl methacrylate.Suitable commercial products are available under the names Dehyquart® CC11 and Luviquat® PQ 11 PN from BASF SE or Gafquat 440, Gafquat 734,Gafquat 755 or Gafquat 755N from Ashland Inc.

Polyquaternium-46 is the reaction product of vinylcaprolactam andvinylpyrrolidone with methylvinylimidazolium methosulfate and isavailable for example under the name Luviquat® Hold from BASF SE.Polyquaternium-46 is preferably used in an amount of about 1 to about 5wt. %—based on the total weight of the cosmetic composition. Itparticularly prefers to use polyquaternium-46 in combination with acationic guar compound. It is even highly preferred thatpolyquaternium-46 is used in combination with a cationic guar compoundand polyquaternium-11.

Suitable anionic film-forming, hydrophilic polymers can be, for example,acrylic acid polymers, which can be in non-crosslinked or crosslinkedform. Such products are sold commercially under the trade names Carbopol980, 981, 954, 2984 and 5984 by Lubrizol or under the names Synthalen Mand Synthalen K by 3V Sigma (The Sun Chemicals, Inter Harz).

Examples of suitable film-forming, hydrophilic polymers from the groupof natural gums are xanthan gum, gellan gum, carob gum.

Examples of suitable film-forming hydrophilic polymers from the group ofpolysaccharides are hydroxyethyl cellulose, hydroxypropyl cellulose,ethyl cellulose and carboxymethyl cellulose.

Suitable film-forming, hydrophilic polymers from the group ofacrylamides are, for example, polymers prepared from monomers of(meth)acrylamido-C1-C4-alkyl sulfonic acid or salts thereof.Corresponding polymers may be selected from the polymers ofpolyacrylamidomethanesulfonic acid, polyacrylamidoethanesulfonic acid,polyacrylamidopropanesulfonic acid,poly2-acrylamido-2-methylpropanesulfonic acid,poly-2-methylacrylamido-2-methylpropanesulfonic acid and/orpoly-2-methylacrylamido-n-butanesulfonic acid.

Preferred polymers of poly(meth)arylamido-C1-C4-alkyl-sulfonic acids arecrosslinked and at least about 90% neutralized. These polymers can becrosslinked or non-crosslinked.

Cross-linked and fully or partially neutralized polymers of thepoly-2-acrylamido-2-methylpropane sulfonic acid type are available underthe INCI names “Ammonium Polyacrylamido-2-methyl-propanesulphonates” or“Ammonium Polyacryldimethyltauramides”.

Another preferred polymer of this type is the crosslinkedpoly-2-acrylamido-2methyl-propanesulfonic acid polymer sold by Clariantunder the trade name Hostacerin AMPS, which is partially neutralizedwith ammonia.

In another explicitly very particularly preferred embodiment, a processis wherein the agent (b) comprises at least one anionic, film-forming,polymer as sealing reagent (b1).

In this context, the best results were obtained when the agent (b)comprises, as sealing reagent (b1), at least one film-forming polymercomprising at least one structural unit of formula (P-I) and at leastone structural unit of formula (P-II)

whereM is a hydrogen atom or ammonium (NH₄), sodium, potassium, ½ magnesiumor ½ calcium.

In a further preferred embodiment, a process as contemplated herein iswherein the agent (b) comprises at least one film-forming polymer assealing reagent (b1), which comprises at least one structural unit ofthe formula (P-I) and at least one structural unit of the formula (P-II)

whereM is a hydrogen atom or ammonium (NH₄), sodium, potassium, ½ magnesiumor ½ calcium.

When M represents a hydrogen atom, the structural unit of the formula(P-I) is based on an acrylic acid unit.

When M stands for an ammonium counterion, the structural unit of theformula (P-I) is based on the ammonium salt of acrylic acid.When M stands for a sodium counterion, the structural unit of theformula (P-I) is based on the sodium salt of acrylic acid.When M stands for a potassium counterion, the structural unit of theformula (P-I) is based on the potassium salt of acrylic acid.

If M stands for a half equivalent of a magnesium counterion, thestructural unit of the formula (P-I) is based on the magnesium salt ofacrylic acid.

If M stands for a half equivalent of a calcium counterion, thestructural unit of the formula (P-I) is based on the calcium salt ofacrylic acid.

The film-forming polymer or polymers are preferably used in specificranges of amounts in the agent (b). In this context, it has provedparticularly preferable for solving the problem as contemplated hereinif the agent (b) comprises—based on the total weight of the agent(b)—one or more film-forming polymers as sealing reagent (b1) in a totalamount of from about 0.1 to about 18 wt. %, preferably from about 1 toabout 16 wt. %, more preferably from about 5 to about 14.5 wt. % andvery particularly preferably from about 8 to about 12 wt. %.

In a further preferred embodiment, a process is wherein the agent (b)comprises—based on the total weight of the agent (b)—one or morefilm-forming polymers as sealing reagent (b1) in a total amount of fromabout 0.1 to about 18 wt. %, preferably from about 1 to about 16 wt. %,more preferably from about 5 to about 14.5 wt. % and very particularlypreferably from about 8 to about 12 wt. %.

The application of agent (b) comprising a film-forming polymer assealing reagent (b1) is intended to seal and/or fix the colored filminitially produced by the application of agent (a). With application ofthe second agent (b) with a film-forming polymer as sealing reagent(b1), the film-forming polymer (b1) is deposited on the colored filmproduced in the first layer in the form of a further film. Themultilayer film system created in this way exhibits improved resistanceto external influences.

Here, the film produced by the agent (b) comprising a film-formingpolymer as sealing reagent (b1) is preferably not colored itself. Inthis way, it can also be ensured that any abrasion to a certain extentof the second film formed by agent (b) does not lead to any colorchanges in the entire film system. It is therefore particularlypreferred if the agent (b) comprises no or only lesser amounts ofcolorant compounds.

In an alternative embodiment, the sealing reagent (b1) comprises analkalizing agent.

Particularly preferably, the alkalizing agent is selected from the groupof ammonia, C₂-C₆ alkanolamines, basic amino acids, alkali metalhydroxides and alkaline earth metal hydroxides.

In another particularly preferred embodiment, a process is wherein theagent (b) comprises at least one alkalizing agent as sealing reagent(b1), which is selected from the group of ammonia, C₂-C₆ alkanolamines,basic amino acids, alkali metal hydroxides, alkaline earth metalhydroxides, alkali metal silicates, alkali metal metasilicates, alkalineearth metal silicates, alkaline earth metal metasilicates, alkali metalcarbonates and alkaline earth metal carbonates.

It has been found that aftertreatment with an agent (b) comprisingammonia exerts a particularly good influence on improving the washfastness and rub fastness of the dyeings obtained in the process.

In the context of a further very particularly preferred embodiment, amethod is wherein the agent (b) comprises ammonia as sealing reagent(b1).

Satisfactory results were also obtained when agent (b) included at leastone C₂-C₆ alkanolamine as sealing reagent (b1).

The alkanolamines that can be used in agent (b) can be selected, forexample, from the group of primary amines having a C₂-C₆ alkyl parentcarrying at least one hydroxyl group. Preferred alkanolamines areselected from the group formed by 2-aminoethan-1-ol (monoethanolamine),3-aminopropan-1-ol, 4-aminobutan-1-ol, 5-aminopentan-1-ol,1-aminopropan-2-ol, 1-aminobutan-2-ol, 1-aminopentan-2-ol,1-aminopentan-3-ol, 1-aminopentan-4-ol, 3-amino-2-methylpropan-1-ol,1-amino-2-methylpropan-2-ol, 3-aminopropan-1,2-diol,2-amino-2-methylpropan-1,3-diol.

In a further preferred embodiment, a process as contemplated herein iswherein the agent (b) comprises, as sealing reagent (b1), at least onealkalizing agent from the group of alkanolamines, which is preferablyselected from the group of 2-aminoethan-1-ol (monoethanolamine),3-aminopropan-1-ol, 4-aminobutan-1-ol, 5-aminopentan-1-ol,1-aminopropan-2-ol, 1-aminobutan-2-ol, 1-aminopentan-2-ol,1-aminopentan-3-ol, 1-aminopentan-4-ol, 3-amino-2-methylpropan-1-ol,1-amino-2-methylpropan-2-ol, 3-aminopropane-1,2-diol and2-amino-2-methylpropane-1,3-diol.

Likewise, satisfactory results were obtained when agent (b) included atleast one basic amino acid as sealing reagent (b1).

For the purposes of the present disclosure, an amino acid is an organiccompound comprising in its structure at least one protonatable aminogroup and at least one —COOH or one —SO₃H group. Preferred amino acidsare aminocarboxylic acids, especially α-(alpha)-aminocarboxylic acidsand ω-aminocarboxylic acids, whereby α-aminocarboxylic acids areparticularly preferred.

As contemplated herein, basic amino acids are those amino acids whichhave an isoelectric point pI of greater than about 7.0.

Basic α-aminocarboxylic acids contain at least one asymmetric carbonatom. In the context of the present disclosure, both enantiomers can beused equally as specific compounds or their mixtures, especially asracemates. However, it is particularly advantageous to use the naturallypreferred isomeric form, usually in L-configuration.

The basic amino acids are preferably selected from the group formed byarginine, lysine, ornithine and histidine, especially preferablyarginine and lysine. In a further particularly preferred embodiment, themethod is therefore wherein the sealing reagent (b1) is an alkalizingagent comprising a basic amino acid selected from the group of arginine,lysine, ornithine and/or histidine.

In a further preferred embodiment, the method is wherein the agent (b)comprises as sealing reagent (b1) at least one alkalizing agent selectedfrom the group of basic amino acids, which is preferably selected fromthe group of arginine, lysine, ornithine and histidine.

Satisfactory results were also obtained when the agent (b) included atleast one alkali metal hydroxide as sealing reagent (b1). Examples ofwell-suited alkali metal hydroxides are sodium hydroxide and potassiumhydroxide.

Satisfactory results were also obtained when the agent (b) included, assealing reagent (b1), an alkalizing agent comprising at least onealkaline earth metal hydroxide. Suitable alkaline earth metal hydroxidesinclude magnesium hydroxide, calcium hydroxide and barium hydroxide.

Satisfactory results were also obtained when the agent (b) included atleast one alkali metal silicate and/or alkali metal metasilicate assealing reagent (b1). Suitable alkali metal silicates include sodiumsilicate and potassium silicate. Suitable alkali metal metasilicatesinclude sodium metasilicate and potassium metasilicate.

Satisfactory results were also obtained when the agent (b) included atleast one alkali metal carbonate and/or alkaline earth metal carbonateas sealing reagent (b1). Suitable alkali metal carbonates include sodiumcarbonate and potassium carbonate. Suitable alkaline earth metalcarbonates include magnesium carbonate and calcium carbonate.

Within the group of the sealing reagents (b1) in the form of analkalizing agent, ammonia, C₂-C₆ alkanolamines, basic amino acids andalkali metal hydroxides have proved to be particularly suitable.

In the context of a further particularly preferred embodiment, theprocess is wherein the agent (b) comprises as sealing reagent (b1) atleast one alkalizing agent selected from the group of ammonia, C₂-C₆alkanolamines, basic amino acids and alkali metal hydroxides.

In another particularly preferred embodiment, the process is wherein theagent (b) comprises, as sealing reagent (b1), at least one alkalizingagent selected from the group of ammonia, 2-aminoethan-1-ol,3-aminopropan-1-ol, 4-aminobutan-1-ol, 5-aminopentan-1-ol,1-aminopropan-2-ol, 1-aminobutan-2-ol, 1-aminopentan-2-ol,1-aminopentan-3-ol, 1-aminopentan-4-ol, 3-amino-2-methylpropan-1-ol,1-amino-2-methylpropan-2-ol, 3-aminopropane-1,2-diol,2-amino-2-methylpropane-1,3-diol, arginine, lysine, ornithine,histidine, sodium hydroxide and potassium hydroxide.

The agent (b) comprises the alkalizing agent as a sealing reagent (b1)in a cosmetic carrier, preferably in an aqueous cosmetic carrier.

In this context, it has been found preferable if the agent (b)comprises—based on the total weight of the agent (b)—about 5.0 to about99.0 wt. %, preferably about 15.0 to about 97.0 wt. %, more preferablyabout 25.0 to about 97.0 wt. %, still more preferably about 35.0 toabout 97.0 wt. % and very particularly preferably about 45.0 to about97.0 wt. % of water.

In the context of a further embodiment, the process is wherein the agent(b) comprises—based on the total weight of the agent (b)—about 5.0 toabout 99.0 wt. % preferably about 15.0 to about 97.0 wt. %, morepreferably about 25.0 to about 97.0 wt. % still more preferably about35.0 to about 97.0 wt. % and very particularly preferably about 45.0 toabout 97.0 wt. % of water.

The alkalizing agents included in the agent (b) exert an influence onthe pH value of the agent (b). It was found that certain alkaline pHvalues have a beneficial effect on the dyeing performance achievable inthe process and the fastness properties of the dyeings.

For this reason, it is preferred that the agent (b) comprising analkalizing agent as sealing reagent (b1) has a pH of from about 7.0 toabout 12.0, preferably from about 7.5 to about 11.5, more preferablyfrom about 8.0 to about 11.0, and most preferably from about 8.5 toabout 9.5.

The pH value can be measured using the usual methods known from thestate of the art, such as pH measurement using glass electrodes viacombination electrodes or using pH indicator paper.

In another very particularly preferred embodiment, the process iswherein the agent (b) comprises an alkalizing agent as sealing reagent(b1) and has a pH of from about 7.0 to about 12.0, preferably from about7.5 to about 11.5, more preferably from about 8.0 to about 11.0 and mostpreferably from about 8.5 to about 9.5.

The pH values for the purposes of the present disclosure are pH valuesmeasured at a temperature of about 22° C.

In a still further alternative embodiment, the sealing reagent (b1)comprises an acidifying agent.

Particularly preferably, the acidifying agent is selected from the groupof inorganic acids, organic acids and mixtures thereof.

Satisfactory results could be obtained when agent (b) comprises at leastone inorganic acid as sealing reagent (b1). Suitable inorganic acidsare, for example, phosphoric acid, sulfuric acid and/or hydrochloricacid, with sulfuric acid being particularly preferred.

In a further preferred embodiment, the process is wherein the agent (b)comprises, as sealing reagent (b1), at least one acidifying agentselected from the group of inorganic acids, which is preferably selectedfrom the group of phosphoric acid, sulfuric acid, hydrochloric acid andmixtures thereof.

In a further, even more preferred embodiment, the method is wherein theagent (b) comprises sulfuric acid as sealing reagent (b1).

Satisfactory results were also obtained when agent (b) included at leastone organic acid as sealing reagent (b1). The organic acid is preferablyselected from the group of formic acid, acetic acid, propionic acid,butyric acid, isobutyric acid, valeric acid, isovaleric acid, pivalicacid, oxalic acid, malonic acid, succinic acid, glutaric acid, glycericacid, Glyoxylic acid, adipic acid, pimelic acid, corkic acid, azelaicacid, sebacic acid, propiolic acid, crotonic acid, isocrotonic acid,elaidic acid, maleic acid, fumaric acid, muconic acid, citraconic acid,mesaconic acid, camphoric acid, benzoic acid, o,m,p-phthalic acid,naphthoic acid, toluoylic acid, hydratropic acid, atropic acid, cinnamicacid, isonicotinic acid, nicotinic acid, bicarbamic acid,4,4′-dicyano-6,6′-binicotinic acid, 8-carbamoyloctanoic acid,1,2,4-pentanetricarboxylic acid, 2-pyrrolecarboxylic acid,1,2,4,6,7-napthalenepentaacetic acid, malonaldehyde acid,4-hydroxy-phthalamic acid, 1-pyrazolecarboxylic acid, gallic acid orpropane tricarboxylic acid, glycolic acid, gluconic acid, lactic acid,maleic acid, ascorbic acid, malic acid, tartaric acid, citric acid andmixtures thereof.

In a further preferred embodiment, the method is wherein the agent (b)comprises as sealing reagent (b1) at least one acidifying agent selectedfrom the group of organic acids, wherein the organic acid is preferablyselected from the group of formic acid, acetic acid, propionic acid,butyric acid, isobutyric acid, valeric acid, isovaleric acid, pivalicacid, oxalic acid, malonic acid, succinic acid, glutaric acid, glycericacid, glyoxylic acid, adipic acid, pimelic acid, corkic acid, azelaicacid, sebacic acid, propiolic acid, crotonic acid, isocrotonic acid,elaidic acid, Maleic acid, fumaric acid, muconic acid, citraconic acid,mesaconic acid, camphoric acid, benzoic acid, o,m,p-phthalic acid,naphthoic acid, toluoylic acid, hydratropasic acid, atropasic acid,cinnamic acid, isonicotinic acid, nicotinic acid, bicarbamic acid,4,4′-dicyano-6,6′-binicotinic acid, 8-carbamoyloctanoic acid,1,2,4-pentane tricarboxylic acid, 2-pyrrole carboxylic acid,1,2,4,6,7-napthalene pentaacetic acid, malonaldehyde acid,4-hydroxy-phthalamic acid, 1-pyrazole carboxylic acid, gallic acid orpropane tricarboxylic acid, glycolic acid, gluconic acid, lactic acid,maleic acid, ascorbic acid, malic acid, tartaric acid, citric acid andmixtures thereof.

In a further, even more preferred embodiment, the method is wherein theagent (b) comprises acetic acid as sealing reagent (b1).

Also, suitable acidifiers include methane sulfonic acid and/or1-hydroxyethane-1,1-diphosphonic acid.

Within the group of the above-mentioned sealing reagents (b1) in theform of an acidifying agent, sulfuric acid and/or acetic acid haveproved to be particularly suitable.

In the context of a further particularly preferred embodiment, theprocess is wherein the agent (b) comprises as sealing reagent (b1) atleast one acidifying agent selected from the group of sulfuric acid,acetic acid and mixtures thereof.

The agent (b) comprises the acidifying agent as sealing reagent (b1) ina cosmetic carrier, preferably in an aqueous cosmetic carrier.

The acidifying agents included in the agent (b) exert an influence onthe pH of the agent (b). It was found that acidic pH values also have abeneficial effect on the dyeing performance achievable in the processand the fastness properties of the dyeings.

For this reason, it is preferred that the agent (b) comprising anacidifying agent as sealing reagent (b1) has a pH of from about 2.0 toabout 6.5, preferably from about 3.0 to about 6.0, more preferably fromabout 4.0 to about 6.0, and most preferably from about 4.5 to about 5.5.

The pH value can be measured using the usual methods known from thestate of the art, such as pH measurement using glass electrodes viacombination electrodes or using pH indicator paper.

In another very particularly preferred embodiment, the process iswherein the agent (b) comprises an acidifying agent as sealing reagent(b1) and has a pH of from about 2.0 to about 6.5, preferably from about3.0 to about 6.0, more preferably from about 4.0 to about 6.0, and mostpreferably from about 4.5 to about 5.5.

The pH values for the purposes of the present disclosure are pH valuesmeasured at a temperature of about 22° C.

The application of agent (b) is intended to seal and fix the filminitially produced by the application of agent (a).

Other Ingredients in Agents (a) and (b)

The agents (a) and (b) described above may also contain one or moreoptional ingredients.

The agents may also contain one or more surfactants. The termsurfactants refer to surface-active substances. A distinction is madebetween anionic surfactants comprising a hydrophobic residue and anegatively charged hydrophilic head group, amphoteric surfactants, whichcarry both a negative and a compensating positive charge, cationicsurfactants, which in addition to a hydrophobic residue have apositively charged hydrophilic group, and non-ionic surfactants, whichhave no charges but strong dipole moments and are strongly hydrated inaqueous solution.

Zwitterionic surfactants are those surface-active compounds which carryat least one quaternary ammonium group and at least one —COOO— or —SO₃⁽⁻⁾ group in the molecule. Particularly suitable zwitterionicsurfactants are the so-called betaines such as theN-alkyl-N,N-dimethylammonium-glycinate, for example thecocoalkyl-dimethylammoniumglycinate,N-acylaminopropyl-N,N-dimethylammoniumglycinate, for example,cocoacylaminopropyl dimethyl ammonium glycinate, and2-alkyl-3-carboxymethyl-3-hydroxyethyl imidazolines each having 8 to 18C atoms in the alkyl or acyl group, and cocoacylaminoethyl hydroxyethylcarboxymethyl glycinate. A preferred zwitterionic surfactant is thefatty acid amide derivative known under the INCI name cocamidopropylbetaine.

Ampholytic surfactants are surface-active compounds which, in additionto a C₈-C₂₄ alkyl or acyl group in the molecule, contain at least onefree amino group and at least one —COOH or —SO₃H group and can forminternal salts. Examples of suitable ampholytic surfactants areN-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids,N-alkyliminodipropionic acids,N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines,N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoaceticacids each with about 8 to 24 C atoms in the alkyl group. Typicalexamples of amphoteric or zwitterionic surfactants are alkylbetaines,alkylamidobetaines, amino-propionates, aminoglycinate,imidazoliniumbetaines and sulfobetaines.

Particularly preferred ampholytic surfactants areN-cocosalkylaminopropionate, cocosacylaminoethylaminopropionate andC₁₂-C₁₈-acylsarcosine.

The agents may also additionally contain at least one non-ionicsurfactant. Suitable non-ionic surfactants are alkyl polyglycosides aswell as alkylene oxide addition products to fatty alcohols and fattyacids with about 2 to about 30 mol ethylene oxide per mol fatty alcoholor fatty acid. Preparations with suitable properties are also obtainedif they contain as non-ionic surfactants fatty acid esters ofethoxylated glycerol reacted with at least 2 mol ethylene oxide.

In addition, the agents may also contain at least one cationicsurfactant. Cationic surfactants are surfactants, i.e., surface-activecompounds, each with one or more positive charges. Cationic surfactantscontain only positive charges. Usually, these surfactants are composedof a hydrophobic part and a hydrophilic head group, the hydrophobic partusually comprising a hydrocarbon backbone (e.g., comprising one or twolinear or branched alkyl chains) and the positive charge(s) being in thehydrophilic head group. Examples of cationic surfactants are

quaternary ammonium compounds which may carry one or two alkyl chainswith a chain length of about 8 to about 28 carbon atoms as hydrophobicradicals,

quaternary phosphonium salts substituted by one or more alkyl chainshaving a chain length of about 8 to about 28 carbon atoms or

tertiary sulfonium salts.

Furthermore, the cationic charge can also be part of a heterocyclic ring(e.g., an imidazolium ring or a pyridinium ring) in the form of an oniumstructure. In addition to the functional unit carrying the cationiccharge, the cationic surfactant may also contain other unchargedfunctional groups, as is the case for example with esterquats. Thecationic surfactants are used in a total quantity of about 0.1 to about45 wt. %, preferably about 1 to about 30 wt. % and most preferably about1 to about 15 wt. %—based on the total weight of the respective agent.

Furthermore, the agents may also contain at least one anionicsurfactant. Anionic surfactants are surface-active agents withexclusively anionic charges (neutralized by a corresponding countercation). Examples of anionic surfactants are fatty acids, alkylsulphates, alkyl ether sulphates and ether carboxylic acids with 12 to20 C atoms in the alkyl group and up to 16 glycol ether groups in themolecule.

The anionic surfactants are used in a total quantity of about 0.1 toabout 45 wt. %, preferably about 1 to about 30 wt. % and most preferablyabout 1 to about 15 wt. %—based on the total weight of the respectiveagent.

The agent (a) and/or agent (b) may further comprise a matting agent.Suitable matting agents include, for example, (modified) starches,waxes, talc and/or (modified) silicas. The amount of matting agent ispreferably between about 0.1 and about 10 wt. % based on the totalamount of agent (a) or agent (b). Preferably, agent (a) comprises amatting agent.

The agents may also contain other active ingredients, auxiliaries andadditives, such as solvents; fatty ingredients such as C₅-C₃₀ fatty acidtriglycerides, C₅-C₃₀ fatty acid monoglycerides, C₅-C₃₀ fatty aciddiglycerides and/or the hydrocarbons; structurants such as glucose,maleic acid and lactic acid, hair-conditioning compounds such asphospholipids, for example lecithin and cephalins; perfume oils,dimethyl isosorbide and cyclodextrins; fiber structure-improving activeingredients, in particular mono-, di- and oligosaccharides such asglucose, galactose, fructose, fructose and lactose; dyes for coloringthe product; anti-dandruff active ingredients such as piroctone olamine,zinc omadine and climbazole; amino acids and oligopeptides; proteinhydrolysates on an animal and/or vegetable basis, as well as in the formof their fatty acid condensation products or optionally anionically orcationically modified derivatives; vegetable oils; light stabilizers andUV blockers; active ingredients such as panthenol, pantothenic acid,pantolactone, allantoin, pyrrolidinonecarboxylic acids and their salts,and bisabolol; Polyphenols, in particular hydroxycinnamic acids,6,7-dihydroxycoumarins, hydroxybenzoic acids, catechins, tannins,leucoanthocyanidins, anthocyanidins, flavanones, flavones and flavonols;ceramides or pseudoceramides; vitamins, provitamins and vitaminprecursors; plant extracts; Fats and waxes such as fatty alcohols,beeswax, montan wax and kerosene; swelling and penetrating agents suchas glycerol, propylene glycol monoethyl ether, carbonates, hydrogencarbonates, guanidines, ureas and primary, secondary and tertiaryphosphates; opacifiers such as latex, styrene/PVP and styrene/acrylamidecopolymers; pearlescent agents such as ethylene glycol mono- anddistearate as well as PEG-3-distearate; and blowing agents such aspropane-butane mixtures, N₂O, dimethyl ether, CO₂ and air.

The selection of these other substances will be made by the specialistaccording to the desired properties of the agents. Regarding otheroptional components and the quantities of these components used,explicit reference is made to the relevant manuals known to thespecialist. The additional active ingredients and auxiliary substancesare preferably used in the preparations as contemplated herein inquantities of about 0.0001 to about 25 wt. % each, about 0.0005 to about15 wt. %, based on the total weight of the respective agent.

Process for Dyeing Keratinous Materials

In the procedure as contemplated herein, agents (a) and (b) are appliedto the keratinous materials, to human hair. Thus, agents (a) and (b) arethe ready-to-use agents. The agents (a) and (b) are different.

In principle, agents (a) and (b) can be applied simultaneously orsuccessively, whereby successive application is preferred.

The best results were obtained when agent (a) was first applied to thekeratinous materials in a first step and agent (b) was applied in asecond step.

Quite particularly preferred, therefore, is a process for treatingkeratinous material, for coloring keratinous material, in particularhuman hair, comprising the following steps in the order indicated:

-   -   in a first step, applying an agent (a) to the keratinous        material, the agent comprising (a):        (a1) at least one organic silicon compound selected from the        group of silanes having one, two or three silicon atoms, and        (a2) at least one coloring compound comprising at least one        effect pigment comprising α) a substrate platelet and β) a        coating, wherein the coating comprises at least one layer that        has been wet-chemically prepared using a metal alkoxide and an        organosilicon compound having a basic group; and    -   In a second step, applying an agent (b) to the keratinous        material, the agent comprising (b):        (b1) at least one sealing reagent.

Moreover, to impart a high leaching resistance to the dyed keratinousmaterial over a longer period, agents (a) and (b) are particularlypreferably applied within the same dyeing process, which means thatthere is a period of a maximum of several hours between the applicationof agents (a) and (c).

In a further preferred embodiment, the method is wherein agent (a) isapplied first and agent (b) is applied thereafter, the period betweenthe application of agents (a) and (b) being at most about 24 hours,preferably at most about 12 hours and particularly preferably at mostabout 6 hours.

A distinguishing feature of the agent (a) is its content of at least onereactive organic silicon compound (a1). The reactive organic siliconcompound(s) (a1) undergoes an oligomerization or polymerization reactionand thus functionalizes the hair surface as soon as it encounters it. Inthis way, a first, film is formed. The coloring compounds (a2) areincorporated into the film so that it is colored. In the second step ofthe process, a second agent (b) is now applied to the hair. During theapplication of the agent (b) comprising at least one film-formingpolymer as sealing reagent (b1), the latter interacts with the silanefilm and is thus bound to the keratinous materials. During theapplication of agent (b) comprising at least one alkalizing agent oracidifying agent as sealing reagent (b1), the formation of the silanefilm is positively influenced.

In the context of a further form of execution, a procedure comprisingthe following steps in the order indicated is particularly preferred

(1) Application of the agent (a) on the keratinous material,(2) Allow the agent (a) to act for a period of about 10 seconds to about10 minutes, preferably from about 10 seconds to about 5 minutes,(3) if necessary, rinse the keratinous material with water,(4) Application of agent (b) on the keratinous material,(5) Allowing the agent (b) to act for a period of about 30 seconds toabout 30 minutes, preferably from about 30 seconds to about 10 minutes,(6) Rinse the keratinous material with water.

The rinsing of the keratinous material with water in steps (3) and (6)of the process is understood, as contemplated herein, to mean that onlywater is used for the rinsing process, without any other agents otherthan agents (a) and (b).

In step (1), agent (a) is first applied to the keratinous materials, inparticular human hair.

After application, the agent (a) is left to act on the keratinousmaterials. In this context, application times from about 10 seconds toabout 10 minutes, preferably from about 20 seconds to about 5 minutesand especially preferably from about 30 seconds to about 2 minutes onthe hair have proven to be particularly beneficial.

In a preferred embodiment of the process, the agent (a) can now berinsed from the keratinic materials before the agent (b) is applied tothe hair in the subsequent step.

Stains with equally good wash fastnesses were obtained when agent (b)was applied to the keratinous materials that were still exposed to agent(a).

In step (4), agent (b) is now applied to the keratinous materials. Afterapplication, let the agent (b) act on the hair.

Even with a short contact time of the agent (b), the process allows theproduction of dyeings with particularly good intensity and washfastness. Application times from about 10 seconds to about 10 minutes,preferably from about 20 seconds to about 5 minutes and most preferablyfrom about 30 seconds to about 3 minutes on the hair have proven to beparticularly beneficial.

In step (6), the agent (b) (and any agent (a) still present) is nowrinsed out of the keratinous material with water.

In this embodiment, the sequence of steps (1) to (6) preferably takesplace within about 24 hours.

Agent (a) comprises, with the organic silicon compound(s), a class ofhighly reactive compounds that can undergo hydrolysis or oligomerizationand/or polymerization when used. As a result of their high reactivity,these organic silicon compounds form a film on the keratinous material.

To avoid premature oligomerization or polymerization, it is ofconsiderable advantage to the user to prepare the ready-to-use agent (a)only shortly before application.

In yet another embodiment, preferred is a method comprising thefollowing steps in the order indicated.

(1) Preparation of an agent (a) by mixing a first agent (a′) and asecond agent (a″), wherein

the first agent (a′) comprises at least one organic silicon compound(a1) from the group of silanes having one, two or three silicon atoms,and

the second agent (a″) comprises at least one colorant compound (a2)comprising at least one effect pigment comprising α) a substrateplatelet and β) a coating, the coating having at least one layerprepared wet-chemically using a metal alkoxide and an organosiliconcompound having a basic group,(2) Application of the agent (a) on the keratinous material,(3) Allow the agent (a) to act for a period of about 10 seconds to about10 minutes, preferably from about 10 seconds to about 5 minutes,(4) if necessary, rinse the keratinous material with water,(5) Application of agent (b) on the keratinous material,(6) Allowing the agent (b) to act for a period of about 30 seconds toabout 30 minutes, preferably from about 30 seconds to about 10 minutes,(7) Rinse the keratinous material with water.

To be able to provide a formulation that is as stable as possible instorage, the agent (a′) itself is preferably formulated to be low inwater or water-free.

In a preferred embodiment, a multicomponent packaging unit(kit-of-parts) is wherein the agent (a′)—based on the total weight ofthe agent (a′)—comprises a water content of from about 0.001 to about 10wt. %, preferably from about 0.5 to about 9 wt. %, more preferably fromabout 1 to about 8 wt. % and very particularly preferably from about 1.5to about 7 wt. %.

The agent (a″) comprises water. In a preferred embodiment, amulticomponent packaging unit (kit-of-parts) is wherein the agent(a″)—based on the total weight of the agent (a2)—has a water content offrom about 15 to about 100 wt. %, preferably from about 35 to about 100wt. %, more preferably from about 55 to about 100 wt. %, still morepreferably from about 65 to about 100 wt. % and very particularlypreferably from about 75 to about 100 wt. %.

Within this embodiment, the ready-to-use agent (a) is now prepared bymixing agents (a′) and (a″).

For example, the user can first mix or shake the agent (a′) comprisingthe organic silicon compound(s) (a1) with the aqueous effectpigment-comprising agent (a″). The user can now apply this mixture of(a′) and (a″) to the keratinous materials—either immediately after itspreparation or after a short reaction time of about 10 seconds to about20 minutes. Afterwards, the user can apply agent (b) as described above.

The optionally included silicone polymer (a3) may be included in theagent (a′) or in the agent (a″). Preferably, the silicone polymer (a3)is included in the agent (a″).

In yet another embodiment, preferred is a method comprising thefollowing steps in the order indicated.

(1) Preparation of an agent (a) by mixing a first agent (a′) and asecond agent (a″), wherein

the first agent (a′) comprises at least one organic silicon compound(a1) from the group of silanes having one, two or three silicon atomsand furthermore at least one silicone polymer (a3), and

the second agent (a″) comprises at least one colorant compound (a2)comprising at least one effect pigment comprising α) a substrateplatelet and β) a coating, the coating having at least one layerprepared wet-chemically using a metal alkoxide and an organosiliconcompound having a basic group,

(2) Application of the agent (a) on the keratinous material,(3) Allow the agent (a) to act for a period of about 10 seconds to about10 minutes, preferably from about 10 seconds to about 5 minutes,(4) if necessary, rinse the keratinous material with water,(5) Application of agent (b) on the keratinous material,(6) Allowing the agent (b) to act for a period of about 30 seconds toabout 30 minutes, preferably from about 30 seconds to about 10 minutes,(7) Rinse the keratinous material with water.

In the context of a further embodiment, particularly preferred is amethod comprising the following steps in the order indicated.

(1) Preparation of an agent (a) by mixing a first agent (a′) and asecond agent (a″), wherein

the first agent (a′) comprises at least one organic silicon compound(a1) from the group of silanes having one, two or three silicon atoms,and

the second agent (a″) comprises at least one colorant compound (a2)comprising at least one effect pigment comprising α) a substrateplatelet and β) a coating, wherein the coating comprises at least onelayer prepared wet-chemically using a metal alkoxide and anorganosilicon compound having a basic group, and further comprises atleast one silicone polymer (a3),

(2) Application of the agent (a) on the keratinous material,(3) Allow the agent (a) to act for a period of about 10 seconds to about10 minutes, preferably from about 10 seconds to about 5 minutes,(4) if necessary, rinse the keratinous material with water,(5) Application of agent (b) on the keratinous material,(6) Allowing the agent (b) to act for a period of about 30 seconds toabout 30 minutes, preferably from about 30 seconds to about 10 minutes,(7) Rinse the keratinous material with water.

In a further preferred embodiment, a process may also be wherein thesilicone polymer(s) (a3) are provided in a third separately preparedagent (a′″).

Preferred in the context of this further embodiment is a methodcomprising the following steps in the order indicated.

(1) Preparation of an agent (a) by mixing a first agent (a′) and asecond agent (a″) and a third agent (a′″), whereinthe first agent (a′) comprises at least one organic silicon compound(a1) from the group of silanes having one, two or three silicon atoms,andthe second agent (a″) comprises at least one colorant compound (a2)comprising at least one effect pigment comprising α) a substrateplatelet and β) a coating, the coating having at least one layerprepared wet-chemically using a metal alkoxide and an organosiliconcompound having a basic group, andthe third agent (a′″) comprises at least one silicone polymer (a3),(2) Application of the agent (a) on the keratinous material,(3) Allow the agent (a) to act for a period of about 10 seconds to about10 minutes, preferably from about 10 seconds to about 5 minutes,(4) if necessary, rinse the keratinous material with water,(5) Application of agent (b) on the keratinous material,(6) Allowing the agent (b) to act for a period of about 30 seconds toabout 30 minutes, preferably from about 30 seconds to about 10 minutes,(7) Rinse the keratinous material with water.

Multi-Component Packaging Unit (Kit-of-Parts)

To increase user convenience, the user is preferably provided with allthe necessary agents in the form of a multi-component packaging unit(kit-of-parts).

A second subject matter of the present disclosure is therefore amulti-component packaging unit (kit-of-parts) for coloring keratinicmaterial, comprehensively packaged separately from one another

-   -   a first container comprising an agent (a′), wherein the agent        comprises (a′):        -   (a1) at least one organic silicon compound selected from the            group of silanes having one, two or three silicon atoms, and        -   a second container comprising an agent (a″), wherein the            agent comprises (a″):            (a2) at least one coloring compound comprising at least one            effect pigment comprising α) a substrate platelet and β) a            coating, wherein the coating comprises at least one layer            that has been wet-chemically prepared using a metal alkoxide            and an organosilicon compound having a basic group; and

a third container comprising an agent (b), wherein the agent comprises(b):

(b1) at least one sealing reagent,wherein the components (a1), (a2) and (b1) have been disclosed in detailabove.

The organic silicon compounds (a1) from the group of silanes with one,two or three silicon atoms included in the agent (a′) of the kitcorrespond to the organic silicon compounds (a1) that were also used inthe agent (a) of the previously described process.

The color-imparting compounds (a2) included in the agent (a″) of thekit, comprising at least one effect pigment comprising α) a substrateplatelet and β) a coating, the coating having at least one layer whichhas been prepared wet-chemically using a metal alkoxide and anorganosilicon compound having a basic group, correspond to the colorantcompounds (a2) comprising an effect pigment comprising α) a substrateplatelet and β) a coating, the coating having at least one layer whichhas been prepared wet-chemically using a metal alkoxide and anorganosilicon compound having a basic group, which were also used in theagent (a) of the process described above.

The sealing reagent (b1) included in agent (b) of the kit corresponds tothe sealing reagent that was also used in agent (b) of the previouslydescribed method.

In this context, it is again possible to use the optionally includedsilicone polymer (a3) in the agent (a′), in the agent (a″) or in afurther agent (a′″).

In the context of a further embodiment, a multi-component packaging unit(kit-of-parts) for coloring keratinic material is preferably packagedseparately from one another

-   -   a first container comprising an agent (a′), wherein the agent        comprises (a′):        at least one organic silicon compound (a1) from the group of        silanes with one, two or three silicon atoms and furthermore at        least one silicone polymer (a3), and    -   a second container comprising an agent (a″), the agent        comprising (a″):        (a2) at least one coloring compound comprising at least one        effect pigment comprising α) a substrate platelet and β) a        coating, wherein the coating comprises at least one layer that        has been wet-chemically prepared using a metal alkoxide and an        organosilicon compound having a basic group; and

a third container comprising an agent (b), wherein the agent comprises(b):

(b1) at least one sealing reagent,wherein the components (a1), (a2), (a3) and (b1) have been disclosed indetail above.

In the context of a further embodiment, a multi-component packaging unit(kit-of-parts) for coloring keratinic material is preferably packagedseparately from one another

-   -   a first container comprising an agent (a′), wherein the agent        comprises (a′):        at least one organic silicon compound (a1) from the group of        silanes having one, two or three silicon atoms, and    -   a second container comprising an agent (a″), the agent        comprising (a″):        (a2) at least one coloring compound comprising at least one        effect pigment comprising α) a substrate platelet and β) a        coating, wherein the coating comprises at least one layer        wet-chemically prepared using a metal alkoxide and an        organosilicon compound having a basic group, and further        comprises at least one silicone polymer (a3), and    -   a third container comprising an agent (a′″), wherein the agent        (a′″) is a water-comprising cosmetic carrier

a fourth container comprising agent (b), wherein the agent comprises(b):

(b1) at least one sealing reagent,wherein the components (a1), (a2), (a3) and (b1) have been disclosed indetail above.

In this embodiment, agents (a′) and (a″) have a low water content. Toprepare the ready-to-use agent (a), agents (a′), (a″) and (a′″) aremixed. In this case, the agent (a′″) represents a water-comprisingcosmetic carrier.

In the context of a further embodiment, a multi-component packaging unit(kit-of-parts) for coloring keratinic material is preferably packagedseparately from one another

-   -   a first container comprising an agent (a′), wherein the agent        comprises (a′):        at least one organic silicon compound (a1) from the group of        silanes having one, two or three silicon atoms,    -   a second container comprising an agent (a″), wherein the agent        comprises (a″):        (a2) at least one coloring compound comprising at least one        effect pigment comprising α) a substrate platelet and β) a        coating, wherein the coating comprises at least one layer        wet-chemically prepared using a metal alkoxide and an        organosilicon compound having a basic group, and further        comprises at least one silicone polymer (a3), and

a third container comprising an agent (b), wherein the agent comprises(b):

(b1) at least one sealing reagent,wherein the components (a1), (a2), (a3) and (b1) have been disclosed indetail above.

In the context of a further embodiment, a multi-component packaging unit(kit-of-parts) for coloring keratinic material is preferably packagedseparately from one another

-   -   a first container comprising an agent (a′), wherein the agent        comprises (a′):        at least one organic silicon compound (a1) from the group of        silanes having one, two or three silicon atoms,    -   a second container comprising an agent (a″), the agent        comprising (a″):        (a2) at least one color-imparting compound comprising at least        one effect pigment comprising α) a substrate platelet and β) a        coating, wherein the coating comprises at least one layer        prepared wet-chemically using a metal alkoxide and an        organosilicon compound having a basic group,    -   a third container comprising an agent (a′″), said agent        comprising (a′″):        at least one silicone polymer (a3), and

a fourth container comprising agent (b), wherein the agent comprises(b):

(b1) at least one sealing reagent,wherein the components (a1), (a2), (a3) and (b1) have been disclosed indetail above.

In this embodiment of the multicomponent packaging unit, it is preferredthat the agent (a′″) further comprises at least one further colorantcompound (a2).

Concerning the further preferred embodiments of the multicomponentpackaging unit, mutatis mutandis what has been said about the processapplies.

EXAMPLES Example 1

The following formulations have been produced (unless otherwiseindicated, all figures are in wt. %)

Agent (a‘) Agent (a‘) wt..-% (3-Aminopropyl)triethoxysilane (a1) 20Methyltrimethoxysilane (a1) 70 Water ad 100

Agent (a“) Agent (a“) wt..-% Effect pigment according to claim 1 (a2) 5PEG-12 Dimethicone (a3) 5 Hydroxyethyl cellulose 1 Water ad 100

The ready-to-use agent (a) was prepared by mixing 5 g of agent (a′) and20 g of agent (a″). The pH value of the agent (a) was adjusted to avalue of 10.5 by adding ammonia or lactic acid. Then the agent (a) wasallowed to stand for about 5 minutes.

Agent (b) Agent (b) wt..-% Ethylene/Sodium Acrylate Copolymer (b1) 40(25% solution) Water ad 100

The agent (a) was massaged into one strand of hair at a time (Kerling,Euronatural hair white), and left to act for 1 minute. The agent (a) wasthen rinsed with water.

Subsequently, agent (b) was applied to the hair strand, left to act for1 minute and then also rinsed with water.

While at least one exemplary embodiment has been presented in theforegoing detailed description, it should be appreciated that a vastnumber of variations exist. It should also be appreciated that theexemplary embodiment or exemplary embodiments are only examples, and arenot intended to limit the scope, applicability, or configuration of thevarious embodiments in any way. Rather, the foregoing detaileddescription will provide those skilled in the art with a convenient roadmap for implementing an exemplary embodiment as contemplated herein. Itbeing understood that various changes may be made in the function andarrangement of elements described in an exemplary embodiment withoutdeparting from the scope of the various embodiments as set forth in theappended claims.

What is claimed is:
 1. The process for dyeing keratinous materialcomprising the following steps: applying an agent (a) to the keratinousmaterial, wherein the agent (a) comprises: (a1) at least one organicsilicon compound chosen from silanes having one, two or three siliconatoms, and (a2) at least one coloring compound comprising at least oneeffect pigment comprising α) a substrate platelet and β) a coating,wherein the coating comprises at least one layer wet-chemically preparedusing a metal alkoxide and an organosilicon compound having a basicgroup, and applying an agent (b) to the keratinous material, wherein theagent (b) comprises: (b1) at least one sealing reagent.
 2. Processaccording to claim 1, wherein the agent (a) comprises at least oneorganic silicon compound (a1) of the formula (I) and/or (II)R₁R₂N-L-Si(OR₃)_(a)(R₄)_(b)  (I), where R₁, R₂ independently represent ahydrogen atom or a C₁-C₆ alkyl group, L is a linear or branched divalentC₁-C₂₀ alkylene group, R₃, R₄ independently of one another represent aC₁-C₆ alkyl group, a, stands for an integer from 1 to 3, and b standsfor the integer 3−a, and wherein in the organic silicon compound offormula (II)(R₅O)_(c)(R₆)_(d)Si-(A)_(e)-[NR₇-(A′)]_(f)-[O-(A″)]_(g)-[NR₈-(A′″)]_(h)-Si(R₆′)_(d′)(OR₅′)_(c′)  (II),R₅, R₅′, R₅″, R₆, R₆′ and R₆″ independently represent a C₁-C₆ alkylgroup, A, A′, A″, A′″ and A″″ independently represent a linear orbranched divalent C₁-C₂₀ alkylene group, R₇ and R₈ independentlyrepresent a hydrogen atom, a C₁-C₆ alkyl group, a hydroxy C₁-C₆ alkylgroup, a C₂-C₆ alkenyl group, an amino C₁-C₆ alkyl group or a group offormula (III)-(A″″)—Si(R₆″)_(d)″(OR₅″)_(c)″  (III), c, stands for an integer from 1to 3, d stands for the integer 3−c, c′ stands ‘for an integer from 1 to3, d′ stands for the integer 3−c′, c″ stands, for an integer from 1 to3, d″ stands for the integer 3−c″, e stands for 0 or 1, f stands for 0or 1, g stands for 0 or 1, h stands for 0 or 1, provided that at leastone of the radicals e, f, g and h is different from
 0. 3. The methodaccording to claim 1, wherein the agent (a) comprises at least oneorganic silicon compound (a1) of formula (I),R₁R₂N-L-Si(OR₃)_(a)(R₄)_(b)  (I), where R₁, R₂ both represent a hydrogenatom, and L represents a linear, bivalent C₁-C₆-alkylene group, R₃, R₄independently represent a methyl group or an ethyl group, a stands forthe number 3 and b stands for the number
 0. 4. The agent according toclaim 1, wherein the agent (a) comprises at least one organic siliconcompound (a1) of formula (I) chosen from (3-Aminopropyl)triethoxysilane(3-Aminopropyl)trimethoxysilane 1-(3-Aminopropyl)silantriol(2-Aminoethyl)triethoxysilane (2-Aminoethyl)trimethoxysilane1-(2-Aminoethyl)silantriol (3-Dimethylaminopropyl)triethoxysilane(3-Dimethylaminopropyl)trimethoxysilane1-(3-Dimethylaminopropyl)silantriol(2-Dimethylaminoethyl)triethoxysilane(2-dimethylaminoethyl)trimethoxysilane, and1-(2-Dimethylaminoethyl)silantriol.
 5. The process according to claim 1,wherein the agent (a) comprises at least one organic silicon compound(a1) of formula (II).(R₅O)_(c)(R₆)_(d)Si-(A)_(e)-[NR₇-(A′)]_(f)-[O-(A″)]_(g)-[NR₈-(A′″)]_(h)-Si(R₆′)_(d′)(OR₅′)_(c′)  (II),where e and f both stand for the number 1, g and h both stand for thenumber 0, A and A′ independently represent a linear, bivalent C₁-C₆alkylene and R₇ represents a hydrogen atom, a methyl group, a2-hydroxyethyl group, a 2-alkenyl group, a 2-aminoethyl group or a groupof formula (III).
 6. The process according to claim 1, wherein the agent(a) comprises at least one organic silicon compound (a1) of formula (II)chosen from3-(Trimethoxysilyl)-N-[3-(trimethoxysilyl)propyl]-1-propanamine3-(Triethoxysilyl)-N-[3-(triethoxysilyl) propyl]-1-propanamineN-Methyl-3-(trimethoxysilyl)-N-[3-(trimethoxysilyl)propyl]-1-propanamineN-Methyl-3-(triethoxysilyl)-N-[3-(triethoxysilyl)propyl]-1-propane amine2-[Bis[3-(trimethoxysilyl)propyl]amino]-ethanol2-[Bis[3-(triethoxysilyl) propyl]amino]-ethanol3-(Trimethoxysilyl)-N,N-bis[3-(trimethoxysilyl) propyl]-1-propanamine3-(Triethoxysilyl)-N,N-bis[3-(triethoxysilyl) propyl]-1-propanamineN1,N1-Bis[3-(trimethoxysilyl)propyl]-1,2-ethanediamine,N1,N1-Bis[3-(triethoxysilyl)propyl]-1,2-ethanediamine,N,N-Bis[3-(trimethoxysilyl)propyl]-2-propen-1-amine andN,N-Bis[3-(triethoxysilyl)propyl]-2-propen-1-amine.
 7. The processaccording to claim 1, wherein the agent (a) comprises at least oneorganic silicon compound (a1) of formula (IV).R₉Si(OR₁₀)_(k)(R₁₁)_(m)  (IV), where R₉ stands for a C₁-C₁₈ alkyl group,R₁₀ represents a hydrogen atom or a C₁-C₆ alkyl group, R₁₁ represents aC₁-C₆ alkyl group k is an integer from 1 to 3, and m stands for theinteger 3−k.
 8. The process according to claim 1, wherein the agent (a)comprises at least one organic silicon compound (a1) of formula (IV)chosen from Methyltrimethoxysilane MethyltriethoxysilaneEthyltrimethoxysilane Ethyltriethoxysilane PropyltrimethoxysilanePropyltriethoxysilane Hexyltrimethoxysilane HexyltriethoxysilaneOctyltrimethoxysilane Octyltriethoxysilane Dodecyltrimethoxysilane,Dodecyltriethoxysilane, Octadecyltrimethoxysilane,Octadecyltriethoxysilane and Mixtures of these.
 9. The process accordingto claim 1, wherein the agent (a) comprises at least two structurallydifferent organic silicon compounds (a1).
 10. The process of claim 1,wherein the substrate platelet comprises aluminum.
 11. The process ofclaim 1, wherein the metal alkoxide comprises a silicon alkoxide chosenfrom tetramethyl orthosilicate, tetraethyl orthosilicate, tetraisopropylorthosilicate, and mixtures thereof.
 12. The process of claim 1, whereinthe organosilicon compound having a basic group comprises a silanehaving one, two or three silicon atoms, which further comprises one ormore basic chemical groups and one or more hydroxyl groups orhydrolysable groups per molecule.
 13. The process according to claim 1,wherein the organosilicon compound having a basic group is chosen from(3-Aminopropyl)triethoxysilane (3-Aminopropyl)trimethoxysilane1-(3-Aminopropyl)silantriol (2-Aminoethyl)triethoxysilane(2-Aminoethyl)trimethoxysilane 1-(2-Aminoethyl)silantriol(3-Dimethylaminopropyl)triethoxysilane(3-Dimethylaminopropyl)trimethoxysilane1-(3-Dimethylaminopropyl)silantriol(2-Dimethylaminoethyl)triethoxysilane(2-Dimethylaminoethyl)trimethoxysilane1-(2-Dimethylaminoethyl)silantriol and Mixtures of these.
 14. Theprocess according to claim 1, wherein the agent (a) comprises at leastone further coloring compound (a2) chosen from colored metal oxides,metal hydroxides, metal oxide hydrates, silicates, metal sulfides,complex metal cyanides, metal sulfates, bronze pigments, colored mica-or mica-based pigments coated with at least one metal oxide, and a metaloxychloride.
 15. Kit-of-parts for dyeing keratinous material, comprisingseparately packaged a first container comprising an agent (a′), whereinthe agent comprises (a′): (a1) at least one organic silicon compoundchosen from silanes having one, two or three silicon atoms, and a secondcontainer comprising an agent (a″), the agent comprising (a″): (a2) atleast one color-imparting compound comprising at least one effectpigment comprising α) a substrate platelet and β) a coating, wherein thecoating comprises at least one layer prepared wet-chemically using ametal alkoxide and an organosilicon compound having a basic group, athird container comprises an agent (b), wherein the agent comprises (b):(b1) at least one sealing reagent.